U.S. patent application number 14/387102 was filed with the patent office on 2015-02-12 for novel fused naphthalene cyclohetero ring compounds, and methods and uses thereof.
The applicant listed for this patent is Corning Incorporated. Invention is credited to Mingqian He, Jieyu Hu, Weijun Niu, Adama Tandia.
Application Number | 20150045560 14/387102 |
Document ID | / |
Family ID | 48143363 |
Filed Date | 2015-02-12 |
United States Patent
Application |
20150045560 |
Kind Code |
A1 |
He; Mingqian ; et
al. |
February 12, 2015 |
NOVEL FUSED NAPHTHALENE CYCLOHETERO RING COMPOUNDS, AND METHODS AND
USES THEREOF
Abstract
Described herein are heterocyclic organic compounds of following
formulae: More specifically, described herein are fused
heterocyclic naphthalene compounds, polymers based on fused
heterocyclic naphthalene compounds, methods for making these
compounds, and uses thereof. The compounds described have improved
polymerization and stability properties that allow for improved
material processibility for use as organic semiconductors (OSCs).
##STR00001##
Inventors: |
He; Mingqian; (Horseheads,
NY) ; Hu; Jieyu; (Littleton, CO) ; Niu;
Weijun; (Painted Post, NY) ; Tandia; Adama;
(Nelson, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Corning Incorporated |
Corning |
NY |
US |
|
|
Family ID: |
48143363 |
Appl. No.: |
14/387102 |
Filed: |
March 28, 2013 |
PCT Filed: |
March 28, 2013 |
PCT NO: |
PCT/US13/34347 |
371 Date: |
September 22, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61617202 |
Mar 29, 2012 |
|
|
|
Current U.S.
Class: |
548/421 ;
556/413; 556/489; 564/428; 568/33; 568/717 |
Current CPC
Class: |
C08G 2261/3243 20130101;
C07F 7/083 20130101; C08G 2261/3241 20130101; C07C 37/18 20130101;
C08G 61/126 20130101; C08G 2261/51 20130101; H01L 51/0036 20130101;
C07C 303/30 20130101; C08G 2261/95 20130101; C08G 61/124 20130101;
C07D 403/04 20130101; C07D 487/04 20130101; H01L 51/0052 20130101;
H01L 51/0072 20130101; C08G 2261/3229 20130101; C07C 37/18
20130101; C08G 2261/12 20130101; C08G 2261/59 20130101; H01L
51/5012 20130101; H01L 51/0094 20130101; H01L 51/0558 20130101;
H01L 51/0043 20130101; C07D 495/04 20130101; C08G 2261/3246
20130101; C07C 37/16 20130101; C07C 211/57 20130101; C08G 2261/92
20130101; C07C 39/225 20130101 |
Class at
Publication: |
548/421 ;
556/489; 556/413; 568/717; 568/33; 564/428 |
International
Class: |
C07F 7/08 20060101
C07F007/08; H01L 51/00 20060101 H01L051/00; C07C 211/57 20060101
C07C211/57; C07D 403/04 20060101 C07D403/04; C07C 37/16 20060101
C07C037/16; C07C 303/30 20060101 C07C303/30 |
Claims
1. A compound of formula: ##STR00073## wherein each X.sub.1 is
independently NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se,
with the proviso that due to conjugation, X.sub.1 may be bonded to
one or more additional R.sub.1; each X.sub.2 is independently N, P,
As, SiR.sub.1, or CR.sub.1, with the proviso that due to
conjugation, X.sub.2 may be bonded to one or more additional
R.sub.1; y is H, halo, trialkylsilane, optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs; and each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone.
2. The compound of claim 1, wherein the compound is 1a or 1b.
3. The compound of claim 1, wherein the compound is 2a, 2b, or
2c.
4. The compound of claim 1, wherein: X.sub.1 is S, Se, NR.sub.1,
PR.sub.1, AsR.sub.1, SbR.sub.1, O, or Te, with the proviso that due
to conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; X.sub.2 is N or CR.sub.1, with the proviso that due to
conjugation, X.sub.2 may be bonded to one or more additional
R.sub.1; y is H, halo, trialkylsiane, optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted C.sub.2-C.sub.40
alkenyl, optionally substituted C.sub.2-C.sub.40 alkynyl, halo,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, or
B(alkoxy).sub.2; and each R.sub.1 is independently H, halo,
optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted
aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, or optionally substituted
sulfone.
5. The compound of claim 4, wherein each R.sub.1 is independently
H, halo, optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, optionally substituted heterocyclyl, or an
optionally substituted aryl or optionally substituted heteroaryl
from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl,
imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl,
triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or
naphthyridinyl.
6. The compound of claim 1, wherein the hole reorganization energy
is less than 0.35 eV.
7. The compound of claim 6, wherein the hole reorganization energy
is from about 0.05 eV to about 0.35 eV.
8. (canceled)
9. (canceled)
10. (canceled)
11. (canceled)
12. (canceled)
13. (canceled)
14. A method of making a compound of structure: ##STR00074##
comprising allowing a compound of structure: ##STR00075## to
undergo a substitution reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each Z is independently Z.sub.1 or I, each Z.sub.1 is
independently Cl or Br; and each y is independently is H, halo,
trialkylsilane optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs.
15. A method of making a compound of structure: ##STR00076##
comprising allowing a compound of structure: ##STR00077## or
structure: ##STR00078## to undergo a ring cyclization reaction;
wherein each R.sub.1 is independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone; each R.sub.2 is
independently optionally substituted C.sub.1-C.sub.40 alkyl or
optionally substituted aryl; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se, with the
proviso that due to conjugation, X.sub.1 may be bonded to one or
more additional R.sub.1; each Z is independently Z.sub.1 or I, each
Z.sub.1 is independently Cl or Br; and each y is independently H,
halo, trialkylsilane optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs.
16. A method of making a compound of structure: ##STR00079##
comprising allowing a compound of structure: ##STR00080## to
undergo a substitution reaction, wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1, with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; each Z is independently
Z.sub.1 or I, each Z.sub.1 is independently CI or Br; and each y is
independently is H, halo, trialkylsilane optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs.
17. (canceled)
18. A method of making a compound of structure: ##STR00081##
comprising allowing a compound of structure: ##STR00082## to
undergo a substitution reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; and each Z is independently Z.sub.1 or I, each Z.sub.1 is
independently Cl or Br.
19. A method of making a compound of structure: ##STR00083##
comprising allowing a compound of structure: ##STR00084## or
structure: ##STR00085## to undergo a ring cyclization reaction;
wherein each R.sub.1 is independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone; each R.sub.2 is
independently optionally substituted C.sub.1-C.sub.40 alkyl or
optionally substituted aryl; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se, with the
proviso that due to conjugation, X.sub.1 may be bonded to one or
more additional R.sub.1; and each Z is independently Z.sub.1 or I,
each Z.sub.1 is independently Cl or Br; and each y is independently
is H, halo, trialkylsilane optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, optionally substituted sulfone,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2,
B(alkoxy).sub.2, or OTs.
20. A method of making a compound of structure: ##STR00086##
comprising allowing a compound of structure: ##STR00087## to
undergo a substitution reaction, wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1, with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; each Z is independently
Z.sub.1 or I, each Z.sub.1 is independently Cl or Br; and each y is
independently is H, halo, trialkylsilane optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs.
21. (canceled)
22. A method of making a compound of structure: ##STR00088##
comprising allowing a compound of structure: ##STR00089## to
undergo a substitution reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; and each Z is independently Z.sub.1 or I, each Z.sub.1 is
independently CI or Brand each y is independently is H, halo,
trialkylsilane optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs.
23. A method of making a compound of structure: ##STR00090##
comprising allowing a compound of structure: ##STR00091## or
structure: ##STR00092## to undergo a ring cyclization reaction;
wherein each R.sub.1 is independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone; each R.sub.2 is
independently optionally substituted C.sub.1-C.sub.40 alkyl or
optionally substituted aryl; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se, with the
proviso that due to conjugation, X.sub.1 may be bonded to one or
more additional R.sub.1; each Z is independently Z.sub.1 or I, each
Z.sub.1 is independently Cl or Br; and each y is independently is
H, halo, trialkylsilane optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, optionally substituted sulfone,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2,
B(alkoxy).sub.2, or OTs.
24. A method of making a compound of structure: ##STR00093##
comprising allowing a compound of structure: ##STR00094## to
undergo a substitution reaction, wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1, with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; each Z is independently
Z.sub.1 or I, each Z.sub.1 is independently Cl or Br; and each y is
independently is H, halo, trialkylsilane optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs.
25. (canceled)
26. A method of making a compound of structure: ##STR00095##
comprising allowing a compound of structure: ##STR00096## to
undergo a substitution reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; and each Z is independently Z.sub.1 or I, each Z.sub.1 is
independently Cl or Br; and each y is independently is H, halo,
trialkylsilane optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs.
27. A method of making a compound of structure: ##STR00097##
comprising allowing a compound of structure: ##STR00098## or
structure: ##STR00099## to undergo a ring cyclization reaction;
wherein each R.sub.1 is independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone; each R.sub.2 is
independently optionally substituted C.sub.1-C.sub.40 alkyl or
optionally substituted aryl; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se, with the
proviso that due to conjugation, X.sub.1 may be bonded to one or
more additional R.sub.1; and each Z is independently Z.sub.1 or I,
each Z.sub.1 is independently Cl or Br; and each y is independently
is H, halo, trialkylsilane optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide; optionally substituted sulfone,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2,
B(alkoxy).sub.2, or OTs.
28. A method of making a compound of structure: ##STR00100##
comprising allowing a compound of structure: ##STR00101## to
undergo a substitution reaction, wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1, with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; each Z is independently
Z.sub.1 or I, each Z.sub.1 is independently Cl or Br; and each y is
independently is H, halo, trialkylsilane optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs.
29. (canceled)
30. A method of making a compound of structure: ##STR00102##
comprising allowing a compound of structure: ##STR00103## to
undergo a substitution reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; and each Z is independently Z.sub.1 or I, each Z.sub.1 is
independently Cl or Br; and each y is independently is H, halo,
trialkylsilane optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs.
31. A method of making a compound of structure: ##STR00104##
comprising allowing a compound of structure: ##STR00105## or
structure: ##STR00106## to undergo a ring cyclization reaction;
wherein each R.sub.1 is independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone; each R.sub.2 is
independently optionally substituted C.sub.1-C.sub.40 alkyl or
optionally substituted aryl; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se, with the
proviso that due to conjugation, X.sub.1 may be bonded to one or
more additional R.sub.1; and each Z is independently Z.sub.1 or I,
each Z.sub.1 is independently Cl or Br; and each y is independently
is H, halo, trialkylsilane optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, optionally substituted sulfone,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2,
B(alkoxy).sub.2, or OTs.
32. A method of making a compound of structure: ##STR00107##
comprising allowing a compound of structure: ##STR00108## to
undergo a substitution reaction, wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1, with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; each Z is independently
Z.sub.1 or I, each Z.sub.1 is independently Cl or Br; and each y is
independently is H, halo, trialkylsilane optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs.
33. (canceled)
34. A device comprising a compound of claim 1.
35. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn.119 of U.S. Provisional Application Ser. No.
61/617,202 filed on Mar. 29, 2012 the content of which is relied
upon and incorporated herein by reference in its entirety.
FIELD
[0002] Described herein are compositions including heterocyclic
organic compounds. More specifically, described herein are fused
heterocyclic naphthalene compounds, methods for making them, and
uses thereof.
TECHNICAL BACKGROUND
[0003] Highly conjugated organic materials, due to their
interesting electronic and optoelectronic properties, are being
investigated for use in a variety of applications, including
organic semiconductors (OSCs), field effect transistors (FETs),
thin-film transistors (TFTs), organic light-emitting diodes
(OLEDs), electro-optic (EO) applications, as conductive materials,
as two photon mixing materials, as organic semiconductors, and as
non-linear optical (NLO) materials.
[0004] In particular, OSCs have attracted a great amount of
attentions in the research community due to their advantages over
inorganic semiconductors such as processing in any form, exhibiting
a high mechanical flexibility, producing at low cost, and having a
low weight. Polycyclic aromatic compounds, such as oligothiophenes,
acenes, rylenes, phthalocyanens, and polythiophene, have been
widely studied as semiconductor materials.
[0005] Among the organic p-type semiconductors, pentacene exhibits
charge mobilities well above 1 cm.sup.2/Vs in organic field effect
transistor devices. This number has been set up as a bench mark for
new small molecule systems in terms of mobility requirements.
However, due to the continuing need for improved performance and
stability in semiconductor structures, there is an unmet need to
develop better performing OSCs that have improved mobility, are
structurally stable, and applicable to the large number of
potential applications seen in the various high technology
markets.
SUMMARY
[0006] Embodiments comprise a rationally designed a family of
alkyl-substituted fused naphthalene hetero ring materials. The
materials have several advantages in that it is easier to introduce
substituents onto the fused rings allowing for significant
improvement of the polymerization process and the polymer material
processibility; substituents can be introduced to multiple
positions which allows for fine tuning material packing behaviors;
introduction of substituted pyrrole structures into the substituted
naphthalene results in lower reorganization energy and higher
mobility; and introduction of .beta.-substituents on five member
ring increases the material stability.
[0007] A first embodiment comprises a compound of formula:
##STR00002##
wherein each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1, with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; y is H, halo,
trialkylsilane, optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs; and
each R.sub.1 is independently H, halo, optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone.
[0008] In some embodiments, the compound is 1a or 1b. In other
embodiments, the compound is 2a, 2b, or 2c. In some embodiments,
X.sub.1 is NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Se, or Te;
X.sub.2 is N or CR.sub.1; y is H, halo, optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted C.sub.2-C.sub.40
alkenyl, optionally substituted C.sub.2-C.sub.40 alkynyl, halo,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, or
B(alkoxy).sub.2; and each R.sub.1 is independently H, halo,
optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted
aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, or optionally substituted
sulfone.
[0009] In other embodiments, each R.sub.1 is independently H, halo,
optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, optionally substituted heterocyclyl, or an
optionally substituted aryl or optionally substituted heteroaryl
from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl,
imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl,
triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or
naphthyridinyl.
[0010] In some embodiments, for 2a, 2b, or 2c, each X.sub.1 is
independently NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, or Te or Se and
each X.sub.2 is independently N, P, As, SiR.sub.1, or CR.sub.1,
with the proviso that due to conjugation, X.sub.1 and X.sub.2 may
be bonded to one or more additional R.sub.1s. In other embodiments,
for 2a, 2b, or 2c, each X.sub.1 is independently NR.sub.1,
PR.sub.1, AsR.sub.1, Sb, O, S, Se, or Te, with the proviso that due
to conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1 and each X.sub.2 is independently N, P, As, or SiR.sub.1,
with the proviso that due to conjugation, X.sub.2 may be bonded to
one or more additional R.sub.1. In some embodiments, each X.sub.2
is independently N or CR.sub.1, with the proviso that due to
conjugation, X.sub.2 may be bonded to one or more additional
R.sub.1.
[0011] In some embodiments, the compound comprises 1a, 1b, 2a, 2b,
or 2c, and the hole reorganization energy is less than 0.35 eV. In
some embodiments, the hole reorganization energy is from about 0.05
to about 0.35 eV.
[0012] Another embodiment comprises a polymer of formula:
##STR00003##
wherein n is an integer greater than zero; k is from 1 to 10; m is
from 0 to 10; with the proviso that when m is 0, k is null; each
X.sub.1 is independently NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S,
Te, or Se, with the proviso that due to conjugation, X.sub.1 may be
bonded to one or more additional R.sub.1; each X.sub.2 is
independently N, P, As, SiR.sub.1, or CR.sub.1, with the proviso
that due to conjugation, X.sub.2 may be bonded to one or more
additional R.sub.1; y is H, halo, trialkylsilane optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs; each R.sub.1 is independently
H, halo, optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted
aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, or optionally substituted
sulfone; and comonomer comprises an optionally substituted
C.sub.2-C.sub.40 conjugated alkenyl, optionally substituted
C.sub.2-C.sub.40 conjugated cycloalkenyl, optionally substitute
C.sub.2-C.sub.40 conjugated heteroalkenyl, optionally substituted
conjugated C.sub.2-C.sub.40 hetero cyclo alkenyl, optionally
substituted C.sub.6-C.sub.40 aryl, optionally substituted
C.sub.6-C.sub.40 heteroaryl, or:
##STR00004## ##STR00005##
wherein m is 1, 2, or 3; o is 0, 1, 2, or 3; R.sub.c1, R.sub.c2,
R.sub.c3, and R.sub.c4 are independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone.
[0013] In some embodiments, R.sub.c1, R.sub.c2, R.sub.c3, and
R.sub.c4 are independently H, optionally substituted
C.sub.1-C.sub.40 alkyl, C.sub.2-C.sub.40 optionally substituted
alkenyl, optionally substituted C.sub.2-C.sub.40 alkynyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, optionally substituted heterocyclyl, or optionally
substituted phenyl, optionally substituted thiophenyl, optionally
substituted furanyl, optionally substituted pyrrolyl, optionally
substituted imidazolyl, optionally substituted triazolyl,
optionally substituted oxaxolyl, optionally substituted thiazolyl,
optionally substituted naphthalenyl, optionally substituted
isoquinolinyl, optionally substituted quinolinyl, or optionally
substituted naphthyridinyl.
[0014] In some embodiments, for 1a', 1b', 2a', 2b', 2c', or 2d',
X.sub.1 is NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Se, or Te, with
the proviso that due to conjugation, X.sub.1 may be bonded to one
or more additional R.sub.1; X.sub.2 is N or CR.sub.1, with the
proviso that due to conjugation, X.sub.2 may be bonded to one or
more additional R.sub.1; y is H, halo, optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted C.sub.2-C.sub.40
alkenyl, optionally substituted C.sub.2-C.sub.40 alkynyl, halo,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, or
B(alkoxy).sub.2; and each R.sub.1 is independently H, halo,
optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted
aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, or optionally substituted
sulfone. In other embodiments, each R.sub.1 is independently H,
halo, optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, optionally substituted heterocyclyl, or an
optionally substituted aryl or optionally substituted heteroaryl
from the group consisting of phenyl, thiophenyl, furanyl, pyrrolyl,
imidazolyl, triazolyl, oxaxolyl, thiazolyl, pyridinyl, pyrimidinyl,
triazinyl, naphthalenyl, isoquinolinyl, quinolinyl, or
naphthyridinyl.
[0015] In some embodiments, for 1a', 1b', 2a', 2b', 2c', or 2d', n
is from 1 to 500; k is from 1-10; and m is from 0-10; with the
proviso that if m is 0, then k is null. In some embodiments, the
ratio of compound 1a, 1b, 2a, 2b, or 2c to comonomer is from about
10:1 to 1:10.
[0016] Another embodiment comprises a method of synthesizing a
compound comprising:
##STR00006##
comprising respectively allowing a compound of structure:
##STR00007##
to undergo a substation reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, or Se; and each Z is
independently Z.sub.1 or I, each Z.sub.1 is independently Cl or Br,
y is H, halo, trialkylsilane optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, aryl, aryloxy, optionally substituted amino,
carboxyalkyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, halo, acyl, optionally substituted
heteroaryl, optionally substituted heteroaralkyl, heteroaryloxy,
optionally substituted heterocyclyl, thiol, alkylthio,
heteroarylthiol, optionally substituted sulfoxide, optionally
substituted sulfone, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3,
B(OH).sub.2, B(alkoxy).sub.2, or OTs.
[0017] Another embodiment comprises a method of making a compound
of structure:
##STR00008##
comprising respectively allowing a compound of structure:
##STR00009## ##STR00010##
undergo a ring cyclization reaction; wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each R.sub.2 is independently
optionally substituted C.sub.1-C.sub.40 alkyl or optionally
substituted aryl; each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; and each Z is independently Z.sub.1 or I, each Z.sub.1 is
independently Cl or Br.
[0018] Another embodiment comprises a method of making a compound
of structure:
##STR00011##
comprising respectively allowing a compound of structure
##STR00012##
undergo a substitution reaction, wherein each R.sub.1 is
independently H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, optionally substituted aryl, aryloxy, optionally
substituted amino, carboxyalkyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, halo, acyl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone; each X.sub.1 is independently
NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, or Se, with the proviso
that due to conjugation, X.sub.1 may be bonded to one or more
additional R.sub.1; each X.sub.2 is independently N, P, As,
SiR.sub.1, or CR.sub.1, with the proviso that due to conjugation,
X.sub.2 may be bonded to one or more additional R.sub.1; each Z is
independently Z.sub.1 or I, each Z.sub.1 is independently Cl or Br;
and each y is H, halo, optionally substituted C.sub.1-C.sub.40
alkyl, optionally substituted aralkyl, alkoxy, alkylthio,
optionally substituted C.sub.2-C.sub.40 alkenyl, optionally
substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino,
acyloxy, aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, optionally substituted sulfone,
OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2,
B(alkoxy).sub.2, or OTs.
[0019] Another embodiment comprises a method of making a polymer of
structure:
##STR00013##
comprising respectively polymerizing a compound of structure:
##STR00014##
with a compound of structure:
##STR00015##
wherein each y is independently H, halo, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, OTs, or
OTf; each u is independently H, halo, OSO-alkyl, Mg-halo, Zn-halo,
Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, OTs, or OTf; each
R.sub.1 is independently H, halo, optionally substituted
C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl, alkoxy,
alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, or optionally substituted sulfone; each X.sub.1 is
independently NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Te, or Se,
with the proviso that due to conjugation, X.sub.1 may be bonded to
one or more additional R.sub.1; each X.sub.2 is independently N, P,
As, SiR.sub.1, or CR.sub.1, with the proviso that due to
conjugation, X.sub.2 may be bonded to one or more additional
R.sub.1; wherein comonomer comprises an optionally substituted
C.sub.2-C.sub.40 conjugated alkenyl, optionally substituted
C.sub.2-C.sub.40 conjugated cycloalkenyl, optionally substitute
C.sub.2-C.sub.40 conjugated heteroalkenyl, optionally substituted
conjugated C.sub.2-C.sub.40 heterocycloalkenyl, optionally
substituted C.sub.6-C.sub.40 aryl, optionally substituted
C.sub.6-C.sub.40 heteroaryl, or:
##STR00016## ##STR00017##
wherein each m is independently 1, 2, or 3; o is 0, 1, 2, or 3; u
is R.sub.c1, R.sub.c2, R.sub.c3, and R.sub.c4 are independently H,
halo, optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted
aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, or optionally substituted
sulfone.
[0020] Another embodiment comprises a device comprising compound
1a, 1b, 2a, 2b, or 2c. Another embodiment comprises a device
comprising polymer 1a', 1b', 2a', 2b', 2c' or 2d'.
[0021] Additional features and advantages will be set forth in the
detailed description which follows, and in part will be readily
apparent to those skilled in the art from the description or
recognized by practicing the embodiments as described in the
written description and claims hereof, as well as in the appended
drawings.
[0022] It is to be understood that both the foregoing general
description and the following detailed description are merely
exemplary, and are intended to provide an overview or framework for
understanding.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The accompanying drawings are included to provide a further
understanding, and are incorporated in and constitute a part of
this specification.
[0024] FIG. 1 shows the importance the reorganization energy (R.E.)
and the transfer integral in the charge carrier mobility (M). Based
on the various plots shown for transfer integrals from 0.4 to 2.0
eV, it is clear that large increases in the transfer integral do
not yield significant variation in the mobility, unless the
reorganization energies are small.
[0025] FIG. 2 is a schematic diagram showing the internal
reorganization energy (E) as a function of nuclear configuration
(N.C.) for hole transfer from the neutral ground state (100) to a
cationic state (200). The figure shows that E varies as a function
of various internal reorganization components,
.lamda.=.lamda..sub.0+.lamda..sub.+, and the ionization potential
(I.P.), IP=E.sub.+*-E.
DETAILED DESCRIPTION
[0026] Before the present materials, articles, and/or methods are
disclosed and described, it is to be understood that the aspects
described below are not limited to specific compounds, synthetic
methods, or uses as such may, of course, vary. It is also to be
understood that the terminology used herein is for the purpose of
describing particular aspects only and is not intended to be
limiting.
[0027] In this specification and in the claims that follow,
reference will be made to a number of terms that shall be defined
to have the following meanings:
[0028] Throughout this specification, unless the context requires
otherwise, the word "comprise," or variations such as "comprises"
or "comprising," will be understood to imply the inclusion of a
stated integer or step or group of integers or steps but not the
exclusion of any other integer or step or group of integers or
steps.
[0029] It must be noted that, as used in the specification and the
appended claims, the singular forms "a," "an" and "the" include
plural referents unless the context clearly dictates otherwise.
Thus, for example, reference to "a pharmaceutical carrier" includes
mixtures of two or more such carriers, and the like.
[0030] "Optional" or "optionally" means that the subsequently
described event or circumstance can or cannot occur, and that the
description includes instances where the event or circumstance
occurs and instances where it does not.
[0031] Ranges may be expressed herein as from "about" one
particular value, and/or to "about" another particular value. When
such a range is expressed, another aspect includes from the one
particular value and/or to the other particular value. Similarly,
when values are expressed as approximations, by use of the
antecedent "about," it will be understood that the particular value
forms another aspect. It will be further understood that the
endpoints of each of the ranges are significant both in relation to
the other endpoint, and independently of the other endpoint.
[0032] A weight percent of a component, unless specifically stated
to the contrary, is based on the total weight of the formulation or
composition in which the component is included.
[0033] The term "alkyl" refers to a monoradical branched or
unbranched saturated hydrocarbon chain having 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.
This term is exemplified by groups such as methyl, ethyl, n-propyl,
iso-propyl, n-butyl, iso-butyl, t-butyl, n-hexyl, n-decyl,
tetradecyl, and the like.
[0034] The term "substituted alkyl" refers to: (1) an alkyl group
as defined above, having 1, 2, 3, 4 or 5 substituents, typically 1
to 3 substituents, selected from the group consisting of alkenyl,
alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino,
acyloxy, amino, aminocarbonyl, alkoxycarbonylamino, azido, cyano,
halogen, hydroxy, keto, thiocarbonyl, carboxy, carboxyalkyl,
arylthio, heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl,
aryloxy, heteroaryl, aminosulfonyl, aminocarbonylamino,
heteroaryloxy, heterocyclyl, heterocyclooxy, hydroxyamino,
alkoxyamino, nitro, --SO-alkyl, --SO-aryl, --SO-heteroaryl,
--SO.sub.2-alkyl, SO.sub.2-aryl and --SO.sub.2-heteroaryl. Unless
otherwise constrained by the definition, all substituents may
optionally be further substituted by 1, 2, or 3 substituents chosen
from alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy,
halogen, CF.sub.3, amino, substituted amino, cyano, and
--S(O).sub.nR.sub.SO, where R.sub.SO is alkyl, aryl, or heteroaryl
and n is 0, 1 or 2; or (2) an alkyl group as defined above that is
interrupted by 1-10 atoms independently chosen from oxygen, sulfur
and NR.sub.a, where R.sub.a is chosen from hydrogen, alkyl,
cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heteroaryl and
heterocyclyl. All substituents may be optionally further
substituted by alkyl, alkoxy, halogen, CF.sub.3, amino, substituted
amino, cyano, or --S(O).sub.nR.sub.SO, in which R.sub.SO is alkyl,
aryl, or heteroaryl and n is 0, 1 or 2; or (3) an alkyl group as
defined above that has both 1, 2, 3, 4 or 5 substituents as defined
above and is also interrupted by 1-10 atoms as defined above.
[0035] The term "alkylene" refers to a diradical of a branched or
unbranched saturated hydrocarbon chain, having 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms,
typically 1-10 carbon atoms, more typically 1, 2, 3, 4, 5 or 6
carbon atoms. This term is exemplified by groups such as methylene
(--CH.sub.2--), ethylene (--CH.sub.2CH.sub.2--), the propylene
isomers (e.g., --CH.sub.2CH.sub.2CH.sub.2-- and
--CH(CH.sub.3)CH.sub.2--) and the like.
[0036] The term "substituted alkylene" refers to: (1) an alkylene
group as defined above having 1, 2, 3, 4, or 5 substituents
selected from the group consisting of alkyl, alkenyl, alkynyl,
alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino,
aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy,
keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,
heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,
heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,
heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,
--SO-alkyl, --SO-aryl, --SO-heteroaryl, --SO.sub.2-alkyl,
--SO.sub.2-aryl and --SO.sub.2-heteroaryl. Unless otherwise
constrained by the definition, all substituents may optionally be
further substituted by 1, 2, or 3 substituents chosen from alkyl,
carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen,
CF.sub.3, amino, substituted amino, cyano, and --S(O)--R.sub.SO,
where R.sub.SO is alkyl, aryl, or heteroaryl and n is 0, 1 or 2; or
(2) an alkylene group as defined above that is interrupted by 1-20
atoms independently chosen from oxygen, sulfur and NR.sub.a--,
where R.sub.a is chosen from hydrogen, optionally substituted
alkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl and heterocyclyl,
or groups selected from carbonyl, carboxyester, carboxyamide and
sulfonyl; or (3) an alkylene group as defined above that has both
1, 2, 3, 4 or 5 substituents as defined above and is also
interrupted by 1-20 atoms as defined above. Examples of substituted
alkylenes are chloromethylene (--CH(Cl)--), aminoethylene
(--CH(NH.sub.2)CH.sub.2--), methylaminoethylene
(--CH(NHMe)CH.sub.2--), 2-carboxypropylene isomers
(--CH.sub.2CH(CO.sub.2H)CH.sub.2--), ethoxyethyl
(--CH.sub.2CH.sub.2O--CH.sub.2CH.sub.2--), ethylmethylaminoethyl
(--CH.sub.2CH.sub.2N(CH.sub.3)CH.sub.2CH.sub.2--), and the
like.
[0037] The term "aralkyl" refers to an aryl group covalently linked
to an alkylene group, where aryl and alkylene are defined herein.
"Optionally substituted aralkyl" refers to an optionally
substituted aryl group covalently linked to an optionally
substituted alkylene group. Such aralkyl groups are exemplified by
benzyl, phenylethyl, 3-(4-methoxyphenyl)propyl, and the like.
[0038] The term "alkoxy" refers to the group R--O--, where R is an
optionally substituted alkyl or optionally substituted cycloalkyl,
or R is a group --Y--Z, in which Y is optionally substituted
alkylene and Z is optionally substituted alkenyl, optionally
substituted alkynyl; or optionally substituted cycloalkenyl, where
alkyl, alkenyl, alkynyl, cycloalkyl and cycloalkenyl are as defined
herein. Typical alkoxy groups are optionally substituted alkyl-O--
and include, by way of example, methoxy, ethoxy, n-propoxy,
iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy,
n-hexoxy, 1,2-dimethylbutoxy, trifluoromethoxy, and the like.
[0039] The term "alkylthio" refers to the group R.sub.S--S--, where
R.sub.S is as defined for alkoxy.
[0040] The term "alkenyl" refers to a monoradical of a branched or
unbranched unsaturated hydrocarbon group typically having from 2 to
20 carbon atoms, more typically 2 to 10 carbon atoms and even more
typically 2 to 6 carbon atoms and having 1-6, typically 1, double
bond (vinyl). Typical alkenyl groups include ethenyl or vinyl
(--CH.dbd.CH.sub.2), 1-propylene or allyl
(--CH.sub.2CH.dbd.CH.sub.2), isopropylene
(--C(CH.sub.3).dbd.CH.sub.2), bicyclo[2.2.1]heptene, and the like.
In the event that alkenyl is attached to nitrogen, the double bond
cannot be alpha to the nitrogen.
[0041] The term "substituted alkenyl" refers to an alkenyl group as
defined above having 1, 2, 3, 4 or 5 substituents, and typically 1,
2, or 3 substituents, selected from the group consisting of alkyl,
alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl,
acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino,
azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy,
carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol,
alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,
aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,
hydroxyamino, alkoxyamino, nitro, --SO-alkyl, --SO-aryl,
--SO-heteroaryl, --SO.sub.2-alkyl, SO.sub.2-aryl and
--SO.sub.2-heteroaryl. Unless otherwise constrained by the
definition, all substituents may optionally be further substituted
by 1, 2, or 3 substituents chosen from alkyl, carboxy,
carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3,
amino, substituted amino, cyano, and --S(O).sub.nR.sub.SO, where
R.sub.SO is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0042] The term "alkynyl" refers to a monoradical of an unsaturated
hydrocarbon, typically having from 2 to 20 carbon atoms, more
typically 2 to 10 carbon atoms and even more typically 2 to 6
carbon atoms and having at least 1 and typically from 1-6 sites of
acetylene (triple bond) unsaturation. Typical alkynyl groups
include ethynyl, (--CCH), propargyl (or prop-1-yn-3-yl,
--CH.sub.2CCH), and the like. In the event that alkynyl is attached
to nitrogen, the triple bond cannot be alpha to the nitrogen.
[0043] The term "substituted alkynyl" refers to an alkynyl group as
defined above having 1, 2, 3, 4 or 5 substituents, and typically 1,
2, or 3 substituents, selected from the group consisting of alkyl,
alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl,
acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino,
azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy,
carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol,
alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,
aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,
hydroxyamino, alkoxyamino, nitro, --SO-alkyl, --SO-aryl,
--SO-heteroaryl, --SO.sub.2-alkyl, SO.sub.2-aryl and
--SO.sub.2-heteroaryl. Unless otherwise constrained by the
definition, all substituents may optionally be further substituted
by 1, 2, or 3 substituents chosen from alkyl, carboxy,
carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3,
amino, substituted amino, cyano, and --S(O).sub.nR.sub.SO, where
R.sub.SO is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0044] The term "aminocarbonyl" refers to the group
--C(O)NR.sub.NR.sub.N where each R.sub.N is independently hydrogen,
alkyl, aryl, heteroaryl, heterocyclyl or where both R.sub.N groups
are joined to form a heterocyclic group (e.g., morpholino). Unless
otherwise constrained by the definition, all substituents may
optionally be further substituted by 1-3 substituents chosen from
alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy,
halogen, CF.sub.3, amino, substituted amino, cyano, and
--S(O).sub.nR.sub.SO, where R.sub.SO is alkyl, aryl, or heteroaryl
and n is 0, 1 or 2.
[0045] The term "acylamino" refers to the group --NR.sub.NCOC(O)R
where each R.sub.NCO is independently hydrogen, alkyl, aryl,
heteroaryl, or heterocyclyl. Unless otherwise constrained by the
definition, all substituents may optionally be further substituted
by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl,
aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3, amino,
substituted amino, cyano, and --S(O).sub.nR.sub.SO, where R.sub.SO
is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0046] The term "acyloxy" refers to the groups --O(O)C-alkyl,
--O(O)C-cycloalkyl, --O(O)C-aryl, --O(O)C-heteroaryl, and
--O(O)C-heterocyclyl. Unless otherwise constrained by the
definition, all substituents may be optionally further substituted
by alkyl, carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy,
halogen, CF.sub.3, amino, substituted amino, cyano, and
--S(O).sub.nR.sub.SO, where R.sub.SO is alkyl, aryl, or heteroaryl
and n is 0, 1 or 2.
[0047] The term "aryl" refers to an aromatic carbocyclic group of 6
to 20 carbon atoms having a single ring (e.g., phenyl) or multiple
rings (e.g., biphenyl), or multiple condensed (fused) rings (e.g.,
naphthyl or anthryl). Typical aryls include phenyl, naphthyl and
the like.
[0048] Unless otherwise constrained by the definition for the aryl
substituent, such aryl groups can optionally be substituted with
from 1 to 5 substituents, typically 1 to 3 substituents, selected
from the group consisting of alkyl, alkenyl, alkynyl, alkoxy,
cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino,
aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy,
keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,
heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,
heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,
heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,
--SO-alkyl, --SO-aryl, --SO-heteroaryl, --SO.sub.2-alkyl,
SO.sub.2-aryl and --SO.sub.2-heteroaryl. Unless otherwise
constrained by the definition, all substituents may optionally be
further substituted by 1-3 substituents chosen from alkyl, carboxy,
carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3,
amino, substituted amino, cyano, and --S(O).sub.nR.sub.SO, where
R.sub.SO is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0049] The term "aryloxy" refers to the group aryl-O-- wherein the
aryl group is as defined above, and includes optionally substituted
aryl groups as also defined above. The term "arylthio" refers to
the group aryl-S--, where aryl is as defined as above.
[0050] The term "amino" refers to the group --NH.sub.2.
[0051] The term "substituted amino" refers to the group
--NR.sub.wR.sub.w where each R.sub.w is independently selected from
the group consisting of hydrogen, alkyl, cycloalkyl, carboxyalkyl
(for example, benzyloxycarbonyl), aryl, heteroaryl and heterocyclyl
provided that both R.sub.w groups are not hydrogen, or a group
--Y--Z, in which Y is optionally substituted alkylene and Z is
alkenyl, cycloalkenyl, or alkynyl. Unless otherwise constrained by
the definition, all substituents may optionally be further
substituted by 1-3 substituents chosen from alkyl, carboxy,
carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3,
amino, substituted amino, cyano, and --S(O).sub.nR.sub.SO, where
R.sub.SO is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0052] The term "carboxyalkyl" refers to the groups --C(O)O-alkyl
or --C(O)O-cycloalkyl, where alkyl and cycloalkyl, are as defined
herein, and may be optionally further substituted by alkyl,
alkenyl, alkynyl, alkoxy, halogen, CF.sub.3, amino, substituted
amino, cyano, and --S(O).sub.nR.sub.SO, in which R.sub.SO is alkyl,
aryl, or heteroaryl and n is 0, 1 or 2.
[0053] The term "cycloalkyl" refers to carbocyclic groups of from 3
to 20 carbon atoms having a single cyclic ring or multiple
condensed rings. Such cycloalkyl groups include, by way of example,
single ring structures such as cyclopropyl, cyclobutyl,
cyclopentyl, cyclooctyl, and the like, or multiple ring structures
such as adamantanyl, bicyclo[2.2.1]heptane,
1,3,3-trimethylbicyclo[2.2.1]hept-2-yl,
(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl), or carbocyclic groups to
which is fused an aryl group, for example indane, and the like.
[0054] The term "cycloalkenyl" refers to carbocyclic groups of from
3 to 20 carbon atoms having a single cyclic ring or multiple
condensed rings with at least one double bond in the ring
structure.
[0055] The terms "substituted cycloalkyl" or "substituted
cycloalkenyl" refer to cycloalkyl or cycloalkenyl groups having 1,
2, 3, 4 or 5 substituents, and typically 1, 2, or 3 substituents,
selected from the group consisting of alkyl, alkenyl, alkynyl,
alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino,
aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy,
keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,
heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,
heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,
heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,
--SO-alkyl, --SO-aryl, --SO-heteroaryl, --SO.sub.2-alkyl,
SO.sub.2-aryl and --SO.sub.2-heteroaryl. Unless otherwise
constrained by the definition, all substituents may optionally be
further substituted by 1, 2, or 3 substituents chosen from alkyl,
carboxy, carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen,
CF.sub.3, amino, substituted amino, cyano, and
--S(O).sub.nR.sub.SO, where R.sub.SO is alkyl, aryl, or heteroaryl
and n is 0, 1 or 2.
[0056] The term "halogen" or "halo" refers to fluoro, bromo,
chloro, and iodo.
[0057] The term "acyl" denotes a group --C(O)R.sub.CO, in which
R.sub.CO is hydrogen, optionally substituted alkyl, optionally
substituted cycloalkyl, optionally substituted heterocyclyl,
optionally substituted aryl, and optionally substituted
heteroaryl.
[0058] The term "heteroaryl" refers to a radical derived from an
aromatic cyclic group (i.e., fully unsaturated) having 1, 2, 3, 4,
5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms and 1, 2, 3
or 4 heteroatoms selected from oxygen, nitrogen and sulfur within
at least one ring. Such heteroaryl groups can have a single ring
(e.g., pyridyl or furyl) or multiple condensed rings (e.g.,
indolizinyl, benzothiazolyl, or benzothienyl). Examples of
heteroaryls include, but are not limited to, [1,2,4]oxadiazole,
[1,3,4]oxadiazole, [1,2,4]thiadiazole, [1,3,4]thiadiazole, pyrrole,
imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine,
indolizine, isoindole, indole, indazole, purine, quinolizine,
isoquinoline, quinoline, phthalazine, naphthylpyridine,
quinoxaline, quinazoline, cinnoline, pteridine, carbazole,
carboline, phenanthridine, acridine, phenanthroline, isothiazole,
phenazine, isoxazole, phenoxazine, phenothiazine, imidazolidine,
imidazoline, triazole, oxazole, thiazole, naphthyridine, and the
like as well as N-oxide and N-alkoxy derivatives of nitrogen
containing heteroaryl compounds, for example pyridine-N-oxide
derivatives.
[0059] Unless otherwise constrained by the definition for the
heteroaryl substituent, such heteroaryl groups can be optionally
substituted with 1 to 5 substituents, typically 1 to 3 substituents
selected from the group consisting of alkyl, alkenyl, alkynyl,
alkoxy, cycloalkyl, cycloalkenyl, acyl, acylamino, acyloxy, amino,
aminocarbonyl, alkoxycarbonylamino, azido, cyano, halogen, hydroxy,
keto, thiocarbonyl, carboxy, carboxyalkyl, arylthio,
heteroarylthio, heterocyclylthio, thiol, alkylthio, aryl, aryloxy,
heteroaryl, aminosulfonyl, aminocarbonylamino, heteroaryloxy,
heterocyclyl, heterocyclooxy, hydroxyamino, alkoxyamino, nitro,
--SO-alkyl, --SO-aryl, --SO-heteroaryl, --SO.sub.2-alkyl,
SO.sub.2-aryl and --SO.sub.2-heteroaryl. Unless otherwise
constrained by the definition, all substituents may optionally be
further substituted by 1-3 substituents chosen from alkyl, carboxy,
carboxyalkyl, aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3,
amino, substituted amino, cyano, and --S(O).sub.nR.sub.SO, where
R.sub.SO is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0060] The term "heteroaralkyl" refers to a heteroaryl group
covalently linked to an alkylene group, where heteroaryl and
alkylene are defined herein. "Optionally substituted heteroaralkyl"
refers to an optionally substituted heteroaryl group covalently
linked to an optionally substituted alkylene group. Such
heteroaralkyl groups are exemplified by 3-pyridylmethyl,
quinolin-8-ylethyl, 4-methoxythiazol-2-ylpropyl, and the like.
[0061] The term "heteroaryloxy" refers to the group
heteroaryl-O--.
[0062] The term "heterocyclyl" refers to a monoradical saturated or
partially unsaturated group having a single ring or multiple
condensed rings, having from 1 to 40 carbon atoms and from 1 to 10
hetero atoms, typically 1, 2, 3 or 4 heteroatoms, selected from
nitrogen, sulfur, phosphorus, and/or oxygen within the ring.
Heterocyclic groups can have a single ring or multiple condensed
rings, and include tetrahydrofuranyl, morpholino, piperidinyl,
piperazino, dihydropyridino, and the like.
[0063] Unless otherwise constrained by the definition for the
heterocyclyl substituent, such heterocyclyl groups can be
optionally substituted with 1, 2, 3, 4 or 5, and typically 1, 2 or
3 substituents, selected from the group consisting of alkyl,
alkenyl, alkynyl, alkoxy, cycloalkyl, cycloalkenyl, acyl,
acylamino, acyloxy, amino, aminocarbonyl, alkoxycarbonylamino,
azido, cyano, halogen, hydroxy, keto, thiocarbonyl, carboxy,
carboxyalkyl, arylthio, heteroarylthio, heterocyclylthio, thiol,
alkylthio, aryl, aryloxy, heteroaryl, aminosulfonyl,
aminocarbonylamino, heteroaryloxy, heterocyclyl, heterocyclooxy,
hydroxyamino, alkoxyamino, nitro, --SO-alkyl, --SO-aryl,
--SO-heteroaryl, --SO.sub.2-alkyl, --SO.sub.2-aryl and
--SO.sub.2-heteroaryl. Unless otherwise constrained by the
definition, all substituents may optionally be further substituted
by 1-3 substituents chosen from alkyl, carboxy, carboxyalkyl,
aminocarbonyl, hydroxy, alkoxy, halogen, CF.sub.3, amino,
substituted amino, cyano, and --S(O).sub.nR.sub.SO, where R.sub.SO
is alkyl, aryl, or heteroaryl and n is 0, 1 or 2.
[0064] The term "thiol" refers to the group --SH.
[0065] The term "substituted alkylthio" refers to the group --S--
substituted alkyl.
[0066] The term "heteroarylthiol" refers to the group
--S-heteroaryl wherein the heteroaryl group is as defined above
including optionally substituted heteroaryl groups as also defined
above.
[0067] The term "sulfoxide" refers to a group --S(O)R.sub.SO, in
which R.sub.SO is alkyl, aryl, or heteroaryl. "Substituted
sulfoxide" refers to a group --S(O)R.sub.SO, in which R.sub.SO is
substituted alkyl, substituted aryl, or substituted heteroaryl, as
defined herein.
[0068] The term "sulfone" refers to a group --S(O).sub.2R.sub.SO,
in which R.sub.SO is alkyl, aryl, or heteroaryl. "Substituted
sulfone" refers to a group --S(O).sub.2R.sub.SO, in which R.sub.SO
is substituted alkyl, substituted aryl, or substituted heteroaryl,
as defined herein.
[0069] The term "keto" refers to a group --C(O)--.
[0070] The term "thiocarbonyl" refers to a group --C(S)--.
[0071] The term "carboxy" refers to a group --C(O)OH.
[0072] The term "conjugated group" is defined as a linear, branched
or cyclic group, or combination thereof, in which p-orbitals of the
atoms within the group are connected via delocalization of
electrons and wherein the structure can be described as containing
alternating single and double or triple bonds and may further
contain lone pairs, radicals, or carbenium ions. Conjugated cyclic
groups may comprise both aromatic and non-aromatic groups, and may
comprise polycyclic or heterocyclic groups, such as
diketopyrrolopyrrole. Ideally, conjugated groups are bound in such
a way as to continue the conjugation between the thiophene moieties
they connect.
[0073] Disclosed are compounds, compositions, and components that
can be used for, can be used in conjunction with, can be used in
preparation for, or are products of the disclosed methods and
compositions. These and other materials are disclosed herein, and
it is understood that when combinations, subsets, interactions,
groups, etc. of these materials are disclosed that while specific
reference of each various individual and collective combinations
and permutation of these compounds may not be explicitly disclosed,
each is specifically contemplated and described herein. Thus, if a
class of molecules A, B, and C are disclosed as well as a class of
molecules D, E, and F and an example of a combination molecule, A-D
is disclosed, then even if each is not individually recited, each
is individually and collectively contemplated. Thus, in this
example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D,
C-E, and C-F are specifically contemplated and should be considered
disclosed from disclosure of A, B, and C; D, E, and F; and the
example combination A-D. Likewise, any subset or combination of
these is also specifically contemplated and disclosed. Thus, for
example, the sub-group of A-E, B-F, and C-E are specifically
contemplated and should be considered disclosed from disclosure of
A, B, and C; D, E, and F; and the example combination A-D. This
concept applies to all aspects of this disclosure including, but
not limited to, steps in methods of making and using the disclosed
compositions. Thus, if there are a variety of additional steps that
can be performed it is understood that each of these additional
steps can be performed with any specific embodiment or combination
of embodiments of the disclosed methods, and that each such
combination is specifically contemplated and should be considered
disclosed.
[0074] Embodiments comprise a rationally designed a family of
alkyl-substituted fused naphthalene hetero ring materials. The
materials have several advantages in that it is easier to introduce
substituents onto the fused rings allowing for significant
improvement of the polymerization process and the polymer material
processibility; substituents can be introduced to multiple
positions which allows for fine tuning material packing behaviors;
introduction of substituted pyrrole structures into the substituted
naphthalene results in lower reorganization energy and higher
mobility; and introduction of .beta.-substituents on five member
ring increases the material stability.
[0075] In one aspect, described herein are compositions comprising
the formula 1a, 1b, 2a, 2b, or 2c:
##STR00018##
wherein each X.sub.1 is independently NR.sub.1, PR.sub.1,
AsR.sub.1, Sb, O, S, Te, or Se, with the proviso that due to
conjugation, X.sub.1 may be bonded to one or more additional
R.sub.1; each X.sub.2 is independently N, P, As, SiR.sub.1, or
CR.sub.1 with the proviso that due to conjugation, X.sub.2 may be
bonded to one or more additional R.sub.1; y is H, halo,
trialkylsilane, optionally substituted C.sub.1-C.sub.40 alkyl,
optionally substituted aralkyl, alkoxy, alkylthio, optionally
substituted C.sub.2-C.sub.40 alkenyl, optionally substituted
C.sub.2-C.sub.40 alkynyl, aminocarbonyl, acylamino, acyloxy, aryl,
aryloxy, optionally substituted amino, carboxyalkyl, optionally
substituted cycloalkyl, optionally substituted cycloalkenyl, halo,
acyl, optionally substituted heteroaryl, optionally substituted
heteroaralkyl, heteroaryloxy, optionally substituted heterocyclyl,
thiol, alkylthio, heteroarylthiol, optionally substituted
sulfoxide, optionally substituted sulfone, OSO-alkyl, Mg-halo,
Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2, B(alkoxy).sub.2, or OTs.
[0076] Each R.sub.1 is independently H, halo, optionally
substituted C.sub.1-C.sub.40 alkyl, optionally substituted aralkyl,
alkoxy, alkylthio, optionally substituted C.sub.2-C.sub.40 alkenyl,
optionally substituted C.sub.2-C.sub.40 alkynyl, aminocarbonyl,
acylamino, acyloxy, optionally substituted aryl, aryloxy,
optionally substituted amino, carboxyalkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, halo, acyl,
optionally substituted heteroaryl, optionally substituted hetero
aralkyl, heteroaryloxy, optionally substituted heterocyclyl, thiol,
alkylthio, heteroarylthiol, optionally substituted sulfoxide, or
optionally substituted sulfone.
[0077] In some embodiments, y is H, halo, --OSO-alkyl, --Mg-halo,
--Zn-halo, --Sn(alkyl).sub.3, --B(OH).sub.2, or --B(alkoxy).sub.2.
In some embodiments, each R.sub.1 is independently H, optionally
substituted alkyl, optionally substituted alkenyl, optionally
substituted alkynyl, optionally substituted aryl, optionally
substituted heteroaryl, optionally substituted heteroaralkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, optionally substituted heterocyclyl, or aralkyl. In
some embodiments, each R.sub.1 is independently H, optionally
substituted alkyl, optionally substituted alkenyl, optionally
substituted alkynyl, optionally substituted cycloalkyl, optionally
substituted cycloalkenyl, optionally substituted heterocyclyl, or
optionally substituted phenyl, optionally substituted thiophenyl,
optionally substituted furanyl, optionally substituted pyrrolyl,
optionally substituted imidazolyl, optionally substituted
triazolyl, optionally substituted oxaxolyl, optionally substituted
thiazolyl, optionally substituted napthalenyl, optionally
substituted isoquinolinyl, optionally substituted quinolinyl, or
optionally substituted naphthyridinyl.
[0078] In some embodiments, for 2a, 2b, or 2c, each X.sub.1 is
independently NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, or Te, with the
proviso that due to conjugation, X.sub.1 may be bonded to one or
more additional R.sub.1; and each X.sub.2 is independently N, P,
As, SiR.sub.1, or CR.sub.1, with the proviso that due to
conjugation, X.sub.2 may be bonded to one or more additional
R.sub.1. In other embodiments, for 2a, 2b, or 2c, each X.sub.1 is
independently NR.sub.1, PR.sub.1, AsR.sub.1, Sb, O, S, Se, or Te,
with the proviso that due to conjugation, X.sub.1 may be bonded to
one or more additional R.sub.1 and each X.sub.2 is independently N,
P, As, or SiR.sub.1, with the proviso that due to conjugation,
X.sub.2 may be bonded to one or more additional R.sub.1.
[0079] In another aspect, the composition comprises formula 1a',
1b', 2a', 2b', 2c', or 2d':
##STR00019##
wherein n is an integer greater than zero; X.sub.1, X.sub.2, y, and
R.sub.1 all have the same meanings as above; k is from 1 to 10 with
the proviso that when m is 0 (meaning no comonomer is present), k
is null (meaning that the "k" term vanishes as it would become
equivalent to the "n" term--therefore the polymer comprises "n"
fused heterocyclic naphthalene groups as described by 1a', 1b',
2a', 2b', 2c', or 2d'); m is from 0 to 10; the ratio of k to m may
be from 1:10 to 10:1 with the exception that when m is 0 the ratio
of k to m is null; and n is from about 1 to 500. In some
embodiments, k is 1, 2 or 3. In some embodiments, m is 1, 2, or 3.
In some embodiments, the ratio of k to m is from about 3:1 to about
1:3. In some embodiments, n is from about 3 to about 20, about 3 to
about 15, about 3 to about 12, about 3 to about 10, or about 5 to
about 9. In some embodiments, n is about 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 60, 70, 80,
90, 100, 150, 200, 250, 300, 350, 400, 450, or 500.
[0080] Comonomer, as used herein, describes a conjugated system
such as any aromatic structure, double or triple bonds, or
conjugated structures. Examples of comonomers include, but are not
limited to:
##STR00020## ##STR00021##
wherein each m is independently is 1, 2, or 3; o is 0, 1, 2, or 3;
R.sub.c1, R.sub.c2, R.sub.c3, and R.sub.c4 are independently H,
halo, optionally substituted C.sub.1-C.sub.40 alkyl, optionally
substituted aralkyl, alkoxy, alkylthio, optionally substituted
C.sub.2-C.sub.40 alkenyl, optionally substituted C.sub.2-C.sub.40
alkynyl, aminocarbonyl, acylamino, acyloxy, optionally substituted
aryl, aryloxy, optionally substituted amino, carboxyalkyl,
optionally substituted cycloalkyl, optionally substituted
cycloalkenyl, halo, acyl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, heteroaryloxy, optionally
substituted heterocyclyl, thiol, alkylthio, heteroarylthiol,
optionally substituted sulfoxide, or optionally substituted
sulfone. In some embodiments, R.sub.c1, R.sub.c2, R.sub.c3, and
R.sub.c4 are independently H, optionally substituted alkyl,
optionally substituted alkenyl, optionally substituted alkynyl,
optionally substituted aryl, optionally substituted heteroaryl,
optionally substituted heteroaralkyl, optionally substituted
cycloalkyl, optionally substituted cycloalkenyl, optionally
substituted heterocyclyl, or aralkyl. In some embodiments,
R.sub.c1, R.sub.c2, R.sub.c3, and R.sub.c4 are independently H,
optionally substituted alkyl, optionally substituted alkenyl,
optionally substituted alkynyl, optionally substituted cycloalkyl,
optionally substituted cycloalkenyl, optionally substituted
heterocyclyl, or optionally substituted phenyl, optionally
substituted thiophenyl, optionally substituted furanyl, optionally
substituted pyrrolyl, optionally substituted imidazolyl, optionally
substituted triazolyl, optionally substituted oxaxolyl, optionally
substituted thiazolyl, optionally substituted napthalenyl,
optionally substituted isoquinolinyl, optionally substituted
quinolinyl, or optionally substituted naphthyridinyl.
[0081] In another aspect, embodiments may be produced through a
series of synthetic steps. For illustrative purposes, reaction
Schemes 1-7 depicted below provide potential routes for
synthesizing the embodiments as well as key intermediates. The
methods disclosed in the instant Schemes and Examples are intended
for purposes of exemplifying only and are not to be construed as
limitations thereon.
[0082] Those skilled in the art will appreciate that other
synthetic routes may be used to synthesize the inventive compounds.
Some aspects of some embodiments may be synthesized by synthetic
routes that include processes analogous to those well-known in the
chemical arts, particularly in light of the description contained
herein. Although specific starting materials and reagents are
depicted in the schemes and discussed below, other starting
materials and reagents can be easily substituted to provide a
variety of derivatives and/or reaction conditions. The starting
materials are generally available from commercial sources, such as
Aldrich Chemicals (Milwaukee, Wis.), or are readily prepared using
methods well known to those skilled in the art (e.g., prepared by
methods generally described in Louis F. Fieser and Mary Fieser,
REAGENTS FOR ORGANIC SYNTHESIS, v. 1-19, Wiley, New York (1967-1999
ed.), or BEILSTEINS HANDBUCH DER ORGANISCHEN CHEMIE, 4, Aufl. ed.
Springer-Verlag, Berlin, including supplements (also available via
the Beilstein online database)). In addition, many of the compounds
prepared by the methods described below can be further modified in
light of this disclosure using conventional chemistry well known to
those skilled in the art.
[0083] In another aspect, compounds comprising 1a, 1b, 2a, 2b, or
2c and intermediates leading to 1a, 1b, 2a, 2b, or 2c may be
synthesized. Scheme 1 exemplifies one possible synthetic routes for
forming embodied compounds 1a and 1b:
##STR00022##
wherein y, X.sub.1 and R.sub.1 have the same meanings as above
(X.sub.2 is shown as --CH, but could be generalized to any
X.sub.2), PG represents a protecting group, such as Me, MOM
(methoxymethyl), EOM (ethoxymethyl), MTM (methylthiomethoxy), THP
(tetrahydropyranyl), etc., each Z is independently Z.sub.1 or I,
each Z.sub.1 is independently Cl or Br, each SO.sub.2R.sub.x is
independently SO.sub.2(CF.sub.2).sub.xF, wherein x is from 1-20,
Ts, or Ms.
[0084] As noted in Scheme 1, a naphthalene diol compound, (1), may
be reacted with N-bromosuccinimide in THF at a 1:2 ratio, and
quenched with saturated sodium thiosulfate to produce
1,5-dibromonaphthalene-2,6-diol, (2). Compound (2) may be reacted
with an alcohol protecting group, such as excess
chloro(methoxy)methane in dichloromethane and
diisopropylethylamine, and quenched with water after 22 hours.
After extraction, 1-5-dibromo-2,6-bis(PG)naphthalene, (3), may be
obtained. Compounds of form (3) may be combined with n-butyl
lithium (2.4 equiv) in an organic solvent, then combined with a
halo-alkyl, such as iodomethane, in THF, extracted with saturated
sodium sulfate, washed, dried, and purified to give
3,7,-dibromo-2,6-bis(PG)-1,5-dialkylnaphthalene, compound (4).
[0085] Compounds of form (5) may be formed via halogenation of
compound (4). The general reaction for iodination is shown below
and is very similar to bromination of (4), except that I.sub.2
could be used instead of CF.sub.2BrCF.sub.2Br:
##STR00023##
For example, compound (4) may be combined with n-BuLi (2.4 eq.) in
solvent (e.g., anhydrous ethyl ether) at room temperature. After
sufficient time, the solution can be cooled to 0.degree. C. and a
THF solution of diiodine (I.sub.2) added. The resulting mixture is
allowed to warm to room temperature over time, quenched, and the
aqueous layer extracted. The combined organic extracts can be
washed and dried to give compound (5) ((5b) in the case of
diiodine). After evaporation, the resulting crude product can be
purified by column chromatography on silica gel.
[0086] Compounds of structure (6),
3,7-dihalo-1,5-dialkylnaphthalene-2,6-diol, may be produced from
compound (5) by combining (5) with 6N HCl in
dichloromethane/methanol (1:18 ratio), heating, stirring overnight,
pouring into water, and extracting with ethyl acetate.
[0087] Compounds of structure (7a),
3,7-Dihalo-1,5-dialkylnaphthalene-2,6-diyl
bis(trifluoromethanesulfonate), may be formed by reaction of
compound (6) in an organic solvent, such as pyridine and
dichloromethane, with trifluoromethanesulfonic anhydride (1:2),
mixed with water and 1M HCl, extracted with dichloromethane and
concentrated in vacuo. The residue may then be purified to give
compound (7a) at about 80% yield.
[0088] Compounds (7b) may be formed from compounds (6) by adding
Tetrakis(triphenylphosphine)palladium(0) ((Pd(PPh3)4), CuI,
triethylamine, diisopropylamine and terminal alkynes to a degassed
solution of (6), stirring at 80.degree. C., and adding water and 1M
HCl after approximately 15 minutes. The resulting mixture can be
extracted and the combined organic layers dried and concentrated to
give (7b) (see, e.g., Zhao, Y.; et al. 15 CHEM. EUR. J. 13356
(2009)), incorporated by reference in its entirety).
[0089] Compounds (8a) may be formed from compounds (7a) by adding
bis(triphenyphosphine) palladium chloride
((Pd(PPh.sub.3).sub.2Cl.sub.2), CuI, and terminal alkynes to a
degassed solution of (7a) in solvent (e.g., THF or DMF), stirring
at room temperature, and adding water and 1M HCl after
approximately 1 hour. The resulting mixture can be extracted and
the combined organic layers dried and concentrated to give (8a)
(see, e.g. Shinamura, S. et al. 133 J. AM. CHEM. SOC. 5024 (2011),
incorporated by reference in its entirety).
[0090] Compounds of structures (8b) may be formed by reaction of
compound (7b) in an organic solvent, such as pyridine and
dichloromethane, with trifluoromethanesulfonic anhydride (1:2),
mixed with water and 1M HCl, extracted with dichloromethane and
concentrated in vacuo. The residue may then be purified to give
compound (8b) (see, e.g. Shinamura, S. et al. 133 J. AM. CHEM. SOC.
5024 (2011), incorporated by reference in its entirety).
[0091] When Z.sub.1 is Br, Compound (9a) may be formed from
compound (8a) via reaction of (8a) with tBuONa,
tris(dibenzylideneacetone)dipalladium(0), and
2,2'-bis(diphenylphosphino)-1,1'-binaphthyl in dry solvent. Primary
amines may be added via a syringe and the mixture was refluxed
under nitrogen for 4 h. After cooling to room temperature, water
can be added to the solution and the reaction mixture extracted.
After drying and solvent evaporation, the residue may be purified
to give compound (9a) (see, e.g., Lu et al., 160 SYN. METALS
1438-41 (2010), incorporated by reference in its entirety).
[0092] In the case wherein x is NHR and Z.sub.1 is Cl, compound
(9a) may be formed from compound (8a) via combination with aryl
chloride, amine, KOtBu and a catalyst in 1,2-dimethoxyethane. The
mixture may be stirred at room temperature in an air atmosphere and
monitored by GC/GC-MS. The reaction may be quenched with water,
extracted with solvent, dried, concentrated and purified to give
the desired product (see, e.g., Lee et al., 13 ORG. LETT. 5540
(2011), incorporated by reference in its entirety).
[0093] Compound (9b) may be formed from compound (8b) via reaction
of (8b) with Cs.sub.2CO.sub.3,
Tris(dibenzylideneacetone)dipalladium(0), and
2,2'-bis(diphenylphosphino)-1,1'-binaphthyl in dry solvent. Primary
amines may be added via a syringe and the mixture was refluxed
under nitrogen for 4 h. After cooling to room temperature, water
can be added to the solution and the reaction mixture extracted.
After drying and solvent evaporation, the residue may be purified
to give compound (9b).
[0094] Alternatively, compound (9b) may be formed from compound
(8b) via reaction of (8b) with Si(SH)(i-Pr).sub.3 in solvent
(Thompson et al., 21 BIOORG. MED. CHEM. LETT. 3764-66 (2011),
herein incorporated by reference), as noted below:
##STR00024##
wherein R.sub.2 is an alkyl or aryl.
[0095] Compounds (10a) and (10b) may be formed from compounds (9a)
and (9b), respectively, via a number of ring cyclization processes.
The first comprises combining in a dried pressure tube either
compound (9a) or (9b) in DMSO or an alternative solvent with finely
crushed KOH. The resulting reaction mixture was heated at
120.degree. C. for 17 hours and was extracted with ethyl acetate,
dried, concentrated and purified by column chromatography (see,
e.g., Verma et al., 13 ORG. LETT. (2011), incorporated by reference
in its entirety). The second comprises combining (9a) or (9b) with
a ruthenium catalyst in dry/deoxygenated solvent (e.g., THF) in a
scintillation vial under an inert atmosphere, such as in a glove
box. The mixture can then be sealed and heated (.about.70.degree.
C.) for an extended period of time (.about.2 days), while being
monitored for completion of the reaction. The resulting products
may be purified by column chromatography (see, e.g., Nair et al.,
16 CHEM. EUR. J. 7992 (2010), incorporated by reference in its
entirety). A third possible method involves (9a) or (9b) with
triethylamine and CuI in a solvent (e.g., DMF) under an inert
atmosphere (e.g., a Schlenk line). The flask may then be sealed and
heated with reaction progress monitored by gas chromatography. The
reaction products may be purified, for example, by adsorbing
directly onto a Teledyne Isco silica load cartridge followed by
elution onto a Teledyne Isco column using a 0 to 20% ethyl
alcohol/hexane solution (see, e.g., Arnold et al., 13 ORG. LETT.
5576 (2011), incorporated by reference in its entirety). Another
method of forming compounds (10a) and (10b) from compounds (9a) and
(9b) comprises reacting (9b) or (9a) with NaOH in ethyl acetate and
N-methylpyrrolidone at 5C, then allowing the reaction to warm to
room temperature for 30 minutes (WO 2011147690, herein incorporated
by reference in its entirety).
[0096] Alternatively, Compounds (10a) and (10b) may be formed from
compounds (8a) and (8b), respectively, using a number of different
methods. The first is the general cyclization procedure for
dibromodiethynylnaphthalene analogues described in Shoji et al.,
133 J. AMER. CHEM Soc. 5024-5035 (2011) (incorporated by reference
in its entirety). The procedure combines Na.sub.2S in NMP with (8a)
or (8b) and heating to about 185.degree. C. for about 12 hours,
then adding the solution to a saturated aqueous ammonium chloride
solution to precipitate. The precipitate is collected by
filtration, washed, and purified by vacuum sublimation to give
(10a) or (10b). Second, per Guilarte et al., 13 ORG. LETT.
5100-5103 (2011) (incorporated by reference in its entirety), a
solution of (8a) or (8b) is combined with Pd.sub.2DBA.sub.3,
LiHMDS, and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene
(Xantphos) in dry solvent (e.g., toluene) and stirred under inert
atmosphere for a short time (.about.2 min). Then TIPS-SH can be
added and the mixture stirred at .about.120.degree. C. until all
aryl bromide is consumed as measured by GC-MS. After cooling, TBAF
(3 equivalents) can be added to the mixture and the mixture is
stirred for 2 hours. The resulting products may be extracted and
purified by column chromatography. The third method is similar to
the second, in that it combines a solution of (8a) or (8b) is
combined with Pd.sub.2DBA.sub.3, LiHMDS, and
4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) in dry
solvent (e.g., toluene) and stirred under inert atmosphere for a
short time (.about.2 min), then addition of TIPS-SH. The resulting
solution may be stirred under inert atmosphere in a microwave at
130.degree. C. and 300 W until all aryl bromide is consumed as
measured by GC-MS. Then Cs.sub.2CO.sub.3 can be added to the
mixture and microwave irradiation continued until the reaction is
complete. The resulting products may be extracted and purified by
column chromatography (Guilarte et al., 13 ORG. LETT. 5100-5103
(2011) (incorporated by reference in its entirety)).
[0097] Schemes 2 and 3 are synthetically similar to Scheme 1, but
provide for the synthesis of the 2a, 2b, and 2c:
##STR00025## ##STR00026##
[0098] Wherein R.sub.1, y, Z.sub.1, X.sub.1, and R.sub.x are the
same as described in Scheme 1 (X.sub.2 is shown as --CH, but could
be generalized to any X.sub.2). The reaction schemes for Schemes 2
and 3 are somewhat simpler in that the hydroxide group does not
need to be protected as no R.sub.1 group is being added as in
Scheme 1. Production of compounds (7c)-(10c) and (7d)-(10d) is done
as noted above for (7a)-(10a). Compounds of structures (10c1) and
(10d1), may be formed by reaction of compound (10c) and (10d)
respectively. n-Butyllithium in hexanes (Aldrich) was added
dropwise to a solution of (10c) or (10d) respectively in an organic
solvent, such as tetrahydrafuran, may afford the lithiation product
of (10c) or (10d) respectively, which could be quenched with
electrophilic reagents. After workup, the residue may then be
purified to give either compound (10c1) or compound (10d1) (see,
e.g. Katritzky, A. et al, 53 J. ORG. CHEM. 794 (1988)),
incorporated by reference in its entirety).
[0099] In another aspect, compounds comprising 1a, 1b, 2a, 2b, or
2c and polymer precursors may be produced through a series of
synthetic steps. The embodiments are shown in Scheme 4 as products
(11b1), (11b2), and (11b3) resulting from (10b):
##STR00027##
Wherein R.sub.1 and X.sub.1 are the same as described in Scheme 1
and R.sub.3 is alkyl (X.sub.2 is shown as --CH, but could be
generalized to any X.sub.2). Similarly, polymer precursors (11a1),
(11a2), and (11a3) may be obtained from (10a), (10c), and (10d)
with the appropriate chemical structure using the same synthetic
procedures described below.
[0100] Possible routes from (10b) to (11b1) include the combination
of (10b) (1.5 mmol) with NBS (3.6 mmol) in organic solvent (e.g.,
chloroform), stirring at room temperature for 24 hours, and
subsequent washing (saturated sodium carbonate/water), extraction
(DCM), drying with Na.sub.2SO.sub.4, and purification (Huang et
al., 13 ORG. LETT. 5252 (2011), incorporated by reference in its
entirety) or combination of (10b) with slow addition of PyHBr.sub.3
(1 eq.) in solvent (THF/CHCl.sub.3) and stirring for approx. 30
minutes at 0.degree. C. The reaction is then diluted with
dichloromethane and washed (2.times.100 mL Na.sub.2S.sub.2O.sub.3),
washed with brine, dried over Na.sub.2SO.sub.4, and purified by
flash chromatography (gradient eluent 5% EtOAc/hexanes to 20%
EtOAc/hexanes) (Qi et al., 133 J. AM. CHEM. SOC. 10050 (2011),
incorporated by reference in its entirety, and Luo et al., 5 ORG.
LETT. 4709-12 (2003), incorporated by reference in its
entirety).
[0101] One possible route from (10b) to (11b2) is the combination
of (10b) (5.52 mmol) with n-butyllithium (13.84 mmol, 2.5 M in
hexane, added dropwise) under inert atmosphere in dry solvent
(e.g., 12 mL hexane) at low temperatures (-78.degree. C.), then
allow to warm to room temperature, and subsequently cooled to
-78.degree. C. after about 20 minutes. A solution of
tributylstannyl chloride (16.62 mmol) may be added dropwise, and
then the solution can be brought to room temperature and stirred
overnight. The mixture is then washed and the product washed,
dried, and purified via column chromatography
(dichloromethane:hexane=1:20 (v:v) (containing small amount
triethylamine)) (Peng et al., 23 ADV. MATER. 4554 (2011),
incorporated by reference in its entirety). A second route from
(10b) to (11b2) is the combination of (10b) (1 eq.) with
n-butyllithium (dropwise addition, 2.5 eq.) in
tetramethylpiperidine (2.3 eq.) and THF (20 mL) at -78.degree. C.,
then addition of R.sub.3SnCl (3 eq.) at -78.degree. C. The mixture
may then be quenched with NaHCO.sub.3, extracted with EtOAc, dried
and purified by flash chromatography (Fargeas et al., 9 EUR. J.
ORG. CHEM. 1711-21 (2003), incorporated by reference in its
entirety).
[0102] A first route from (11b1) to (11b2) comprises combining
(11b1) (0.80 mmol) with n-butyllithium (2 mmol) under inert
atmosphere (argon) in dry solvent (THF) at low temperatures
(-78.degree. C.), then allow to warm to room temperature, and
subsequently cooled to -78.degree. C. after about 20 minutes. A
solution of trimethylstannyl chloride (1.2 mmol 1.2 mL hexane) may
be added dropwise, and then the solution can be brought to room
temperature and stirred overnight. The mixture is then quenched
with water, extracted with ether, dried, evacuated in vacuo, and
recrystallized from isopropanol and hexanes (Peng et al., 23 ADV.
MATER. 4554 (2011), incorporated by reference in its entirety). A
second route from (11b1) to (11b2) comprises combining (11b1) with
n-butyllithium (2.98 mmol) in
1-tert-butyl-6-methyl-2-bromo-3-cyclohexyl-1H-indole-1,6-dicarboxylate
(2.29 mmol) and THF (35 mL) at -78.degree. C., then addition of
R.sub.3SnCl (3.43 mmol) at -78.degree. C., then allowing the
mixture to warm to room temperature. The mixture may then be
quenched with H.sub.2O/NaHCO.sub.3, extracted, dried and purified
via flash chromatography (2:98 EtOAc/petroleum ether) (Avolio et
al., 48 J. MED. CHEM. 4547 (2005), incorporated by reference in its
entirety).
[0103] One possible route from (10b) to (11b3) is the combination
of (10b) (3.24 mmol) with n-butyllithium (added dropwise, 2.88
mmol) in THF (35 mL) under inert atmosphere at room temperature and
then stirred at .about.50.degree. C. for 2 hours. Then
2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.1 mmol) may
be added in one portion at room temperature. After .about.6 hours,
the reaction is stopped and the organic layer extracted (diethyl
ether) and purified by column chromatography (Huo et al., 49 ANGEW
CHEM. INT. ED. 1500 (2010), incorporated by reference in its
entirety). A second route from (10b) to (11b3) is the combination
of (1,5-cyclooctadiene)(methoxy)iridium(I) dimmer (0.15 eq.),
4,4'-di-tert-butyl-2,2'-dipyridyl (0.03 eq.),
bis(pinacolato)diboron (2.00 eq.), 10b (1 eq.), and a stirring bar
in a dry flask under argon. To this mixture is added anhydrous
dichloromethane (2.2. mL) to give a colorless suspension and the
flask is heated at 65.degree. C. After .about.3 hours, the mixture
is cooled to 23.degree. C. and volatile removed under reduced
pressure, and then the product is purified by flash chromatography
(Schneider et al., 13 ORG. LETT. 3588 (2011) and Kolundzic et al.,
133 J. AM. CHEM. SOC. 9104-11 (2011), both incorporated by
reference).
[0104] Conversion from (11b1) to (11b3) may be accomplished by a
number of routes. The first involves dissolving (11b1) (1.2 mmol)
in anhydrous THF (25 mL) or an equivalent solvent and cooling to
-78.degree. C., then adding n-butyllithium (2.2. eq.) and stirring.
Next, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 eq.)
may be added and the reaction stirred overnight. The product is
extracted, washed, filtered and the solvent evaporated to give an
oil that may be purified via column chromatography (e.g., 12''
silica column run with cyclohexane/ethyl acetate (4:1)) (Brookins
et al. 19 J. MATER. CHEM. 4197 (2009), incorporated by reference in
its entirety). Alternatively, to a solution of (11b1) (5.0 mmol in
400 mL 1,4-dioxane) may be added pinacolborane (357 mmol), then
triethylamine 476 (mmol) dropwise at room temperature. After
stirring for .about.3 hours, addition of
(2-biphenyl)dicyclohexylphosphine (14.3 mmol) and Pd(OAc).sub.2
(3.57 mmol) is done. The combined mixture is then heated to about
85.degree. C. for about 1.5 hours. Subsequently, a saturated
aqueous NH.sub.4Cl solution is added to the mixture and the product
extracted with EtOAc, washed, dried and filtered, and then
triturated in hexane:EtOAc (20:1) (Ikegashira et al. 49 J. MED.
CHEM. 6950 (2006), incorporated by reference in its entirety).
[0105] In another aspect, compounds comprising 1a', 1b', 2a', 2b',
or 2c' may be produced through a series of synthetic steps.
Compounds may be synthesized by synthetic routes that include
processes analogous to those well-known in the chemical arts,
particularly in light of the description contained herein. Scheme 5
exemplifies one way to form embodied compounds:
##STR00028##
wherein n, X.sub.1, X.sub.2, y, R.sub.1, n and comonomer all have
the same meanings as above, k=m=1, and each Q is independently H,
halo, OSO-alkyl, Mg-halo, Zn-halo, Sn(alkyl).sub.3, B(OH).sub.2,
B(alkoxy).sub.2, OTs, or OTf. Similarly, polymers comprising 1b,
2a, 2b, or 2c may be made using the same synthetic procedures
described herein. If the naphthalene reactant is (10a)-(10d), then
(10a)-(10d) may be combined with dibromide comonomer (1:1 ratio),
trans-di(.mu.-acetato)bis[o-(di-o-tolyl-phosphino)benzyl]dipalladium(II)
(4% mol) and Cs.sub.2CO.sub.3 (2 eq.) and placed in a microwave
vial with a magnetic stirring bar. The vial is then sealed with a
cap and purged with nitrogen to remove the oxygen. THF is added and
the reaction is heated with an oil bath at 120.degree. C. (reaction
under pressure). At the end of the reaction time, the reaction is
cooled and the corresponding 5-alkyl[3,4-c]pyrrole-4,6-dione is
added in excess as a capping agent. The solution was heated again
at 120.degree. C. for 1 hour to complete the end-capping procedure.
After cooling, the mixture is poured in to 500 mL of cold methanol
to precipitate to product. The precipitate is filtered, extracted
via Soxhlet extraction with acetone followed by hexanes to remove
catalytic residue and low MW materials. Polymers may be extracted
with chloroform and then re-precipitated by re-pouring into cold
methanol and filtering (Berrouard et al., 50 ANGEW. CHEM. INT. ED.
1-5 (2011), incorporated by reference in its entirety).
[0106] Alternatively, if the naphthalene reactant is (11b1) or
(11a1), the polymer may be formed by combining (11b2) (or (11a2))
(0.25 mmol) with ditin, or diboranes or diboronate esters
(comonomer) (1:1 eq.) in toluene (15 mL). The solution is flushed
with argon for 10 min, and then Pd.sub.2DBA.sub.3 (2 mol %) and
P(o-tolyl).sub.3 (16.36 mg, 8%) are added into the flask. The flask
is purged, heated to 110.degree. C., and stirred for 48 h under
argon. 2-Tributylstannyl thiophene (20 .mu.L) is then added to the
reaction and after two hours, 2-bromothiophene (6.3 .mu.L) is added
and the mixture is stirred overnight to complete the end-capping
reaction. The mixture is then cooled to room temperature, and the
product filtered, washed with methanol (350 mL) and hexane in a
Soxhlet apparatus to remove the oligomers and catalyst residue.
Finally, the polymer is extracted with chloroform, condensed by
evaporation and precipitated into methanol. The polymer was
collected as a dark purple solid (Peng et al., 23 ADV. MATER. 4554
(2011), incorporated by reference in its entirety and Huo et al.,
49 ANGEW CHEM. INT. ED. 1500 (2010), incorporated by reference in
its entirety).
[0107] A second alternative for Scheme 5 is to start with (11b2) or
(11a2). For example, (11b2) (0.25 mmol) and the dibromide comonomer
(1:1 eq.) are dissolved in toluene (15 mL). The solution is flushed
with argon for 10 min, and then Pd.sub.2DBA.sub.3 (2 mol %) and
P(o-tolyl).sub.3 (16.36 mg, 8%) are added into the flask. The flask
is purged, heated to 110.degree. C., and stirred for 48 h under
argon. 2-Tributylstannyl thiophene (20 .mu.L) is then added to the
reaction and after two hours, 2-bromothiophene (6.3 .mu.L) is added
and the mixture is stirred overnight to complete the end-capping
reaction. The mixture is then cooled to room temperature, and the
product filtered, washed with methanol (350 mL) and hexane in a
Soxhlet apparatus to remove the oligomers and catalyst residue.
Finally, the polymer is extracted with chloroform, condensed by
evaporation and precipitated into methanol. The polymer was
collected as a dark purple solid (Peng et al., 23 ADV. MATER. 4554
(2011), incorporated by reference in its entirety).
[0108] A third alternative for Scheme 3 is to start with (11b3) or
(11a3). For example, (11b3) (0.35 mmol) and dibromide comonomer
(1:1 eq.) are dissolved in toluene (15 mL) with sodium carbonate
(1M, 3 mL). The solution is flushed with argon for 10 min, and then
Pd(PPh.sub.3).sub.4 (15 mg) is added into the flask. The flask is
purged, heated to 110.degree. C., and stirred for 18 h under argon.
The mixture is then cooled to room temperature, and the product
filtered, washed with methanol (100 mL) and hexane in a Soxhlet
apparatus to remove the oligomers and catalyst residue. Finally,
the polymer is extracted with chloroform, condensed by evaporation
and precipitated into methanol. The polymer was collected as a dark
purple solid (Huo et al., 49 ANGEW CHEM. INT. ED. 1500 (2010),
incorporated by reference in its entirety).
[0109] Scheme 6 exemplifies another possible way to form embodied
compounds:
##STR00029##
wherein n, X.sub.1, X.sub.2, y, R.sub.1, n and comonomer all have
the same meanings as above, and k>1 and m>1.
[0110] Starting with (11b1) or (11a1), the polymer in Scheme 6 may
be formed by combining (11ba1) (or (11a1), dibromide comonomer (1:1
eq.), zinc powder (3.1 eq.), triphenyl phosphine (1 eq.),
bipyridine (0.075 eq.), and nickel (II) chloride (0.075 eq.) in a
dry round bottom flask inside of a dry box. The flask is sealed
with a septum and removed from the dry box and anhydrous DMAC is
added via cannulation. The reaction is heated to 85.degree. C. and
after about five minutes, the reaction has a green-yellow color,
with the yellow growing in intensity overtime. The reaction may be
run for 24 hours, and then the polymer is precipitated into
methanol and dried under vacuum.
[0111] Scheme 7 exemplifies another possible way to form embodied
compounds:
##STR00030##
wherein n, X.sub.1, X.sub.2, y, R.sub.1, n and comonomer all have
the same meanings as above, and k>1 and m>1.
[0112] Starting with (11b1) or (11a1), the polymer in Scheme 5 may
be formed by first dissolving (11b1) (or (11a1)) in anhydrous THF
and then adding n-butyllithium (1.2 eq.) and stirring.
2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 eq.) is
added and the reaction stirred overnight. The product was
extracted, washed, dried and evaporated give (11b13), which can be
purified via with cyclohexane/ethyl acetate (4:1) column
chromatography. Compound (11b13) is combined with cesium fluoride
(7 eq.) in a dry flask purged with argon and then the comonomer is
added in degassed solvent (12 mL per mmol of monomer) along with
Pd.sub.2dba.sub.3 (2 mol %) and tri(t-butyl)phosphonium
tetrafluoroborate (6 mol %), and the reaction is refluxed for 48 h.
The polymer is precipitated into methanol and dried under
vacuum.
[0113] Comonomers may be produced by known synthetic methods. Such
methods are shown in, for example, 72 J. ORG. CHEM. 442-451 (2007),
6 BEILSTEIN J. ORG. CHEM. 830-845 (2010), Jerry March, Michael B.
Smith, MARCH'S ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISMS,
AND STRUCTURE (6.sup.th Ed. Wiley-Interscience), Richard C. Larock,
COMPREHENSIVE ORGANIC TRANSFORMATIONS (1999 Wiley-VCH), all hereby
incorporated by reference in their entireties.
[0114] In another aspect, embodiments herein are optimized for
reorganization energy and mobility. In some embodiments, compounds
embodied herein have improved solid state properties as a result of
lower reorganization energy and/or higher mobility. In some
embodiments, the properties of the compounds embodied herein may be
described by Marcus theory (R. A. Marcus, 65 REV. MOD. PHYS. 599
(1993), herein incorporated by reference in its entirety).
[0115] Charge transport properties depend critically on the degree
of ordering of the system or molecular ordering in the solid state,
as well as the density of chemical impurities and/or structural
defects such as grain size and dislocations. At the electronic
level, two of the most important factors that control transport
properties in organic conjugated materials are the interchain
transfer integral .beta., and the reorganization energy .lamda..
The transfer integral expresses the ease of transfer of a charge
between interacting chains. The reorganization energy term
describes the strength of the electron-phonon coupling. It is
proportional to the geometric relaxation energy of the charged
molecule over the individual neutral unit. In the context of
semi-classical electron-transfer theory, the electron-transfer
(hopping) rate can be expressed from Marcus theory in a simplified
way as:
k et = 4 .pi. 2 h 1 4 .pi. k B .lamda. T .beta. 2 - .lamda. 4 k B T
( 1 ) ##EQU00001##
(R. A. Marcus, 65 REV. MOD. PHYS. 599 (1993), herein incorporated
by reference in its entirety) where T is the temperature, .lamda.
is the reorganization energy, .beta. is the transfer integral, and
h and k.sub.B are the Planck and Boltzmann constants,
respectively.
[0116] It is possible to simplify equation (1) to:
k et simple = 1 .lamda. .beta. 2 - .lamda. ( 2 ) ##EQU00002##
In order to characterize the relative influence of both parameters
.lamda. and .beta. to the charge transport rate. FIG. 1
schematically depicts the relationship of mobility (M) as a
function of the reorganization energy (R.E.) at five different
values of the transfer integral (ranging from 0.4 eV to 2 eV). From
FIG. 1, it is clear that the difference in mobility for different
transfer integrals is only significant for small values of the
reorganization energy. A big increase in the transfer integral does
not yield a significant variation in the mobility, unless the
reorganization energies are small. This implies that any
optimization of the mobility should start with the design of single
molecules with very low reorganization energy.
[0117] The reorganization energy includes two contributions that
are associated with charge hopping. One is introduced by the
geometric changes within the single molecule, and is denoted the
internal part. The second one arises from the repolarization
changes of the surrounding medium and is usually much smaller than
the first one. In studies to qualitatively order molecules it is
generally valid to neglect this last contribution in the evaluation
of the reorganization energy as no significant solvent
reorganization occurs during the charge transfer in the condensed
phase.
[0118] Table 1 incorporates reorganization energies for a number of
embodiments. For each molecule, the geometry is optimized using
quantum mechanics for both neutral and ionic states. Consequently,
the basic hopping step in a molecular wire is defined by four
energies: E.sub.0 and E.sub.+ represent the energies of the neutral
and cation species in their lowest energy geometries, respectively,
while E.sub.0* and E.sub.+* represent the energies of the neutral
and cation species with the geometries of the cation and neutral
species, respectively.
[0119] The quantum mechanics calculations to determine these above
mentioned quantities used the experimentally parameterized
Hamiltonian PM6 implemented in VAMP.RTM. semi-empirical molecular
orbital software (Accelrys Software Inc.). Pentacene was used as
the reference to validate the Hole Reorganization Energy
calculations. Experimental data for Pentacene RE was .about.0.12 eV
(see M. Malagoli and J. L. Bredas, 327 CHEM. PHYS. LETT. 13 (2000)
and N. W. Gruhn et al., 89 PHYS. REV. LETT. 275503 (2002), both
hereby incorporated by reference in their entirety), compared to
0.114 eV from our calculations based on VAMP.RTM. (Accelrys
Software Inc.).
[0120] Hole Reorganization energies for embodiments may comprise
from about 0 eV to about 0.5 eV. In some embodiments, the hole
reorganization energy is from about 0.04 to about 0.35 eV. In some
embodiments, the hole reorganization energy is 0.35 eV or less. In
some embodiments, the hole reorganization energy is about 0.04,
0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15,
0.17, 0.19, 0.20, 0.22, 0.25, 0.27, 0.30, 0.31, 0.32, 0.33, 0.34,
0.35, 0.37, 0.40, 0.45, or 0.50.
TABLE-US-00001 Vertical Vertical Ionization Electron Hole Potential
Affinity Reorganization Compound [eV] [eV] Energy [eV] ##STR00031##
6.78 -1.62 0.0766 ##STR00032## 6.82 -.145 0.0792 ##STR00033## 6.75
-2.14 0.113 ##STR00034## 7.45 -2.01 0.112 ##STR00035## 7.75 -1.67
0.114 ##STR00036## 6.80 -1.38 0.117 ##STR00037## 7.53 -2.55 0.119
##STR00038## 6.80 -1.61 0.134 ##STR00039## 7.45 -1.59 0.139
##STR00040## 7.39 -2.01 0.142 ##STR00041## 7.35 -1.74 0.143
##STR00042## 7.52 -2.55 0.158 ##STR00043## 7.29 -2.32 0.159
##STR00044## 7.47 -1.60 0.164 ##STR00045## 7.36 -1.76 0.168
##STR00046## 7.35 -2.55 0.206 ##STR00047## 7.33 -2.33 0.214
##STR00048## 6.93 -2.44 0.228 ##STR00049## 6.94 -2.44 0.27
##STR00050## 6.85 -1.95 0.28 ##STR00051## 7.63 -2.06 0.307
[0121] The compositions described herein (monomers, oligomers,
polymers) can be used to make a wide variety of devices. For
example, the device can be a fused thiophene moiety-containing
composition configured in an electronic, optoelectronic, or
nonlinear optical device. The compositions described herein can
also be used in field effect transistors (FETs), thin-film
transistors (TFTs), organic light-emitting diodes (OLEDs), PLED
applications, electro-optic (EO) applications, as conductive
materials, as two photon mixing materials, as organic
semiconductors, as non-linear optical (NLO) materials, as RFID
tags, as electroluminescent devices in flat panel displays, in
photovoltaic devices, and as chemical or biological sensors.
[0122] The polymers comprising the fused thiophene moieties
described herein (1a', 1b', 2a', 2b', 2c', and 2d') possess several
advantages over similar compounds. The polymers embodied herein are
easier to modify on the designed fused rings, allowing for
improvements in the polymerization process and processibility.
Further, substituents can be introduced to multiple positions which
can enable fine tuning material packing behaviors. The introduction
of substituted pyrrole structures into substituted naphthalene
results in lower reorganization energy and higher mobility for the
compounds and finally .beta.-substituents on the five-member ring
increases the material stability of the resulting polymers.
EXAMPLES
[0123] The following examples are put forth so as to provide those
of ordinary skill in the art with a complete disclosure and
description of how the materials, articles, and methods described
and claimed herein are made and evaluated, and are intended to be
purely exemplary and are not intended to limit the scope. Efforts
have been made to ensure accuracy with respect to numbers (e.g.,
amounts, temperature, etc.) but some errors and deviations should
be accounted for. Unless indicated otherwise, parts are parts by
weight, temperature is in .degree. C. or is at ambient temperature,
and pressure is at or near atmospheric. There are numerous
variations and combinations of reaction conditions, e.g., component
concentrations, desired solvents, solvent mixtures, temperatures,
pressures and other reaction ranges and conditions that can be used
to optimize the product purity and yield obtained from the
described process. Although specific starting materials and
reagents are depicted in the Examples below, other starting
materials and reagents can be easily substituted to provide a
variety of derivatives and/or reaction conditions. In addition,
many of the compounds prepared by the methods described below can
be further modified in light of this disclosure using conventional
chemistry well known to those skilled in the art. Only reasonable
and routine experimentation will be required to optimize such
process conditions.
Example 1
1,5-dibromonaphthalene-2,6-diol
##STR00052##
[0125] To a solution of naphthalene-2,6-diol (1) (5.1 g) in 50 mL
of Tetrahydrofuran (THF), was added N-Bromosuccinimide (NBS, 11.4
g). The mixture was refluxing and monitored by GCMS. The reaction
was quenched with saturated sodium thiosulfate, and filtered. The
solid was washed by water to afford 1,5-dibromonaphthalene-2,6-diol
(90%). LRMS (ESI): Calcd. for C.sub.10H.sub.6Br.sub.2O.sub.2:
317.8714. Found: 317.9.
Example 2
1,5-Dibromo-2,6-bis(methoxymethoxy)naphthalene
##STR00053##
[0127] To a solution of 1,5-dibromonaphthalene-2,6-diol (2) (77.15
g) in dichloromethane (500 mL), diisoprorylethylamine (255 mL) and
chloro(methoxy)methane (MOMCl, 98.6 g) were added at 0.degree. C.
After stirring for 22 h at room temperature, the reaction was
quenched by adding water. The crude products were extracted with
ethyl acetate and the combined organic extracts were washed with
brine, dried over sodium sulfate (Na.sub.2SO.sub.4), and
concentrated in vacuum. The solid residue was stirred in n-hexanes
to afford analytically pure
1,5-dibromo-2,6-bis(methoxymethoxy)naphthalene (90%). LRMS (ESI):
Calcd. for C.sub.14H.sub.14Br.sub.2O.sub.4: 405.9238. Found:
406.0.
Example 3
2,6-bis(methoxymethoxy)-1,5-dimethylnaphthalene
##STR00054##
[0129] 1,5-dibromo-2,6-bis(methoxymethoxy)naphthalene (100 g) was
dissolved in THF (1.6 L) and treated with n-Butyllithium (n-BuLi,
246 mL of 2.5 M solution in hexane, 2.5 e.g.) at -78.degree. C. and
stirred for one hour. The resulting mixture was quenched with
iodomethane (46 mL) for 0.5 hour. The solution was extracted with
ethyl acetate and Na.sub.2S.sub.2O.sub.3 and NaHCO.sub.3. The
mixture was evaporated under reduced vacuum to give the product
1,5-dihexyl-2,6-bis(methoxymethoxy)naphthalene (90%). LRMS (ESI):
Calcd. for C.sub.16H.sub.20O.sub.4: 276.1362. Found: 276.1.
Example 4
3,7-dibromo-2,6-bis(methoxymethoxy)-1,5-dimethylnaphthalene
##STR00055##
[0131] N-BuLi (140 mL of 2.5 M solution) was added at room
temperature to a solution of
2,6-bis(methoxymethoxy)-1,5-dimethylnaphthalene (29 g) in anhydrous
ethyl ether (Et.sub.2O, 1 L). After 3 h, the solution was cooled to
0.degree. C. A THF (100 ml) solution of
1,2-dibromo-1,1,2,2-tetrafluoroethane (108 g) was added to the
above mixture, and the resulting mixture was allowed to warm to
room temperature over 4 h. Saturated sodium thiosulfate was then
added to quench the reaction, and the aqueous layer was extracted
with ethyl acetate. The combined organic extracts were washed with
brine and dried over Na.sub.2SO.sub.4. After evaporation, the
resulting crude product was purified by column chromatography on
silica gel to give the final product
3,7-dibromo-2,6-bis(methoxymethoxy)-1,5-dimethylnaphthalene (45%).
LRMS (ESI): Calcd. for C.sub.16H.sub.18Br.sub.2O.sub.4: 433.9551.
Found: 434.0.
Example 5
3,7-dibromo-1,5-dimethylnaphthalene-2,6-diol
##STR00056##
[0133] A mixture of
3,7-dibromo-2,6-bis(methoxymethoxy)-1,5-dimethyl naphthalene (3 g)
and hydrochloric acid (6N HCl, 30 mL) in dichloromethane/methanol
(15 ml/75 ml) was heated to 50.degree. C. and stirred overnight.
The resulting mixture was poured into water and extracted with
ethyl acetate. The organic extracts were washed with brine and
dried over Na.sub.2SO.sub.4. The solvents were evaporated to give
the crude product 3,7-dibromo-1,5-dimethylnaphthalene-2,6-diol.
(90%). LRMS (ESI): Calcd. for C.sub.12H.sub.10Br.sub.2O.sub.2:
345.9027. Found: 345.9.
Example 6
3,7-Dibromo-1,5-dimethylnaphthalene-2,6-diyl bis(trifluoro
methanesulfonate)
##STR00057##
[0135] To a suspension of
3,7-dibromo-1,5-dimethylnaphthalene-2,6-diol (3.24 g), pyridine
(4.5 mL) in dichloromethane (90 mL) was slowly added
trifluoromethanesulfonic anhydride (3.6 mL) at 0.degree. C. After
the mixture was stirred for 4 h at room temperature, water and
hydrochloric acid (1 M) were added. The resulting mixture was
extracted with dichloromethane and combined organic layer was dried
(MgSO.sub.4) and concentrated in vacuo. The residue was purified by
column chromatography on silica gel to give
3,7-Dibromo-1,5-dimethylnaphthalene-2,6-diyl
bis(trifluoromethanesulfonate) (80%). LRMS (ESI): Calcd. for
C.sub.14H.sub.8Br.sub.2F.sub.6O.sub.6S.sub.2: 609.8013. Found:
609.9.
Example 7
((3,7-dibromo-1,5-dimethylnaphthalene-2,6-diyl)bis(ethyne-2,1-diyl))bis(tr-
iisopropylsilane)
##STR00058##
[0137] To a degassed solution of
3,7-Dibromo-1,5-dimethylnaphthalene-2,6-diyl bis(trifluoro
methanesulfonate) (28 mg) in dimethylformamide (DMF, 1 mL) and
diisopropylamine (0.7 mL) was added bis(triphenylphosphine)
palladium chloride (Pd(PPh.sub.3).sub.2Cl.sub.2, 25 mg), copper(I)
iodide (CuI) (9 mg) and ethynyltriisopropylsilane (70 .mu.L). After
the mixture was stirred for 50 min at room temperature, water and
hydrochloric acid (1 M) were added. The resulting mixture was
extracted with ethyl acetate and the combined organic layer was
dried (MgSO.sub.4) and concentrated in vacuo. The residue was
purified by column chromatography on silica gel to give
((3,7-dibromo-1,5-dimethylnaphthalene-2,6-diyl)bis(ethyne-2,1-diyl))-
bis(triisopropylsilane) (50%). LRMS (ESI): Calcd. for
C.sub.34H.sub.SOBr.sub.2Si.sub.2: 631.1250 (MW-pr). Found: 631.1
(MW-43).
Example 8
4,8-dimethyl-N.sub.2,N.sub.6-dipentyl-3,7-bis((triisopropylsilyl)
ethynyl) naphthalene-2,6-diamine
##STR00059##
[0139] A solution of
((3,7-dibromo-1,5-dimethylnaphthalene-2,6-diyl)bis(ethyne-2,1-diyl))bis(t-
riisopropylsilane) (0.73 mmol), t-NaOBu (304 mg), Pd.sub.2dba.sub.3
(54 mg) and (S)-BINAP (78 mg) in dry toluene (8 mL) was purged with
nitrogen for 10 min. Pentan-1-amine (0.58 ml) was added via a
syringe and the mixture was refluxed under nitrogen for 4 hours.
After cooling to room temperature, water was added to the solution
and the reaction mixture was extracted twice with diethyl ether.
After the organic phases were dried over MgSO.sub.4, the solvents
were removed using a rotary evaporator. The residue was purified by
column chromatography on silica gel to give
4,8-dimethyl-N2,N6-dipentyl-3,7-bis((triisopropylsilyl)ethynyl)naphthalen-
e-2,6-diamine (40%). LRMS (ESI): Calcd. For
C.sub.44H.sub.74N.sub.2Si.sub.2: 686.5391. Found: 686.6.
Example 9
3,7-di(hex-1-yn-1-yl)-1,5-dimethylnaphthalene-2,6-diol
##STR00060##
[0141] Compounds 3,7-dibromo-1,5-dimethylnaphthalene-2,6-diol (560
mg), [Pd(PPh.sub.3).sub.4] (31.0 mg), CuI (24 mg), PPh.sub.3 (31
mg), iPr.sub.2NH (5.8 mL), and Et.sub.3N (16.1 mL) were added to a
three necked flask, equipped with a condenser and a magnetic
stirrer under an inert atmosphere. The mixture was purged with Ar
and stirred for 30 min, while compound hex-1-yne (1.1 mL) was added
in one portion. After the addition, the reaction mixture was slowly
heated to 80.degree. C. and stirred for 15 min at this temperature.
After cooling to room temperature, the solvent was removed under
reduced pressure to afford the residue, which was extracted with
DCM, and washed twice with water. The organic layer was dried
(MgSO.sub.4). After removal of solvent, the product was purified by
flash column chromatography to give
3,7-di(hex-1-yn-1-yl)-1,5-dimethylnaphthalene-2,6-diol (90%). LRMS
(ESI): Calcd. For C.sub.24H.sub.28O.sub.2: 348.2089. Found:
348.2.
Example 10
3,7-di(hex-1-yn-1-yl)-1,5-dimethylnaphthalene-2,6-diyl
bis(trifluoromethanesulfonate)
##STR00061##
[0143] To a suspension of
3,7-di(hex-1-yn-1-yl)-1,5-dimethylnaphthalene-2,6-diol (210 mg),
pyridine (0.3 mL) in dichloromethane (6 mL) was slowly added
trifluoromethanesulfonic anhydride (0.21 mL) at 0.degree. C. After
the mixture was stirred for 2 h at room temperature, water and
hydrochloric acid (1 M) were added. The resulting mixture was
extracted with dichloromethane and combined organic layer was dried
(MgSO.sub.4) and concentrated in vacuo. The residue was purified by
column chromatography to give
3,7-di(hex-1-yn-1-yl)-1,5-dimethylnaphthalene-2,6-diyl
bis(trifluoromethanesulfonate) (40%) LRMS (ESI): Calcd. For
C.sub.26H.sub.26F.sub.6O.sub.6S.sub.2: 612.1075. Found: 612.0.
Example 11
3,7-di(hex-1-yn-1-yl)-1,5-dimethyl-N2,N6-dipentylnaphthalene-2,6-diamine
##STR00062##
[0145] A solution of
3,7-di(hex-1-yn-1-yl)-1,5-dimethylnaphthalene-2,6-diylbis(trifluorometh-a-
nesulfonate) (367 mg), Cs.sub.2CO.sub.3 (960 mg), Pd.sub.2dba.sub.3
(133 mg) and (S)-BINAP (385 mg) in dry toluene (7 ml) was purged
with nitrogen for 20 min. Pentan-1-amine (0.48 mL) was added via a
syringe and the mixture was refluxed under nitrogen for 7 h. After
cooling to room temperature, water was added to the solution and
the reaction mixture was extracted twice with diethyl ether. After
the organic phases were dried over MgSO4, the solvents were removed
using a rotary evaporator. The crude product was purified by column
chromatography and the desired product of
3,7-di(hex-1-yn-1-yl)-1,5-dimethyl-N2,N6-dipentylnaphthalene-2,6-di-amine
was obtained (24%). LRMS (ESI): Calcd. For C.sub.34H.sub.50N.sub.2:
486.3974. Found: 486.4.
Example 12
2,7-dibutyl-5,10-dimethyl-1,6-dipentyl-1,6-dihydroindolo[6,5-1]indole
##STR00063##
[0147] In an dried pressure tube, to a solution of
3,7-di(hex-1-yn-1-yl)-1,5-dimethyl-N.sub.2,N.sub.6-dipentylnaphthalene-2,-
6-diamine (10 mg) in DMSO (2 mL) was added finely crushed KOH (100
mg). The resulting reaction mixture was heated at 120.degree. C.
for 16 h and was extracted with ethyl acetate and the combined
organic layer was dried (MgSO.sub.4) and concentrated in vacuo. The
residue was purified by column chromatography on silica gel to give
4,9-dimethyl-1,6-dipentyl-1,6-dihydroindolo[6,5-f]indole. LRMS
(ESI): LRMS (ESI): Calcd. For C.sub.34H.sub.50N.sub.2: 486.3974.
Found: 486.4.
Example 13
1,5-dibromonaphthalene-2,6-diylbis(trifluoromethanesulfonate)
##STR00064##
[0149] To a suspension of 1,5-dibromonaphthalene-2,6-diol (10.1 g),
pyridine (15.3 mL) in dichloromethane (305 mL) was slowly added
trifluoromethanesulfonic anhydride (12.2 mL) at 0.degree. C. After
the mixture was stirred for 8 h at room temperature, water and
hydrochloric acid (1 M) were added. The resulting mixture was
extracted with dichloromethane and combined organic layer was dried
(MgSO.sub.4) and concentrated in vacuo. The residue was purified by
column chromatography to give 1,5-dibromonaphthalene-2,6-diyl
bis(trifluoromethanesulfonate) (50%) LRMS (ESI): Calcd. For
C.sub.12H.sub.4Br.sub.2F.sub.6O.sub.6S.sub.2: 581.7700. Found:
581.8.
Example 14
1,5-dibromo-2,6-di(hex-1-yn-1-yl)naphthalene
##STR00065##
[0151] To a degassed solution of 1,5-dibromonaphthalene-2,6-diyl
bis(trifluoromethanesulfonate) (582 mg) in DMF (7 mL) and
diisopropylamine (7 mL) was added Pd(PPh.sub.3).sub.2Cl.sub.2 (70
mg), CuI (38 mg) and hex-1-yne (222 .mu.L). Reaction was stirred at
room temperature and monitored by GCMS. Water and hydrochloric acid
(1 M) were added. The resulting mixture was extracted with
dichloromethane and the combined organic layer was dried
(MgSO.sub.4) and concentrated in vacuo. The residue was purified by
column chromatography on silica gel eluted with hexane to give
1,5-dibromo-2,6-di(hex-1-yn-1-yl)naphthalene (50%) LRMS (ESI):
Calcd. For C.sub.22H.sub.22Br.sub.2: 446.2181. Found: 446.1.
Example 15
2,6-di(hex-1-yn-1-yl)-N1,N5-dipentylnaphthalene-1,5-diamine
##STR00066##
[0153] A solution of 1,5-dibromo-2,6-di(hex-1-yn-1-yl)naphthalene
(710 mg), t-BuONa (367 mg), Pd.sub.2dba.sub.3 (73 mg) and (S)-BINAP
(198 mg) in dry toluene (6 ml) was purged with nitrogen for 20 min.
Pentan-1-amine (0.58 mL) was added via a syringe and the mixture
was refluxed under nitrogen for 7 h. After cooling to room
temperature, water was added to the solution and the reaction
mixture was extracted twice with diethyl ether. After the organic
phases were dried over MgSO.sub.4, the solvents were removed using
a rotary evaporator. The crude product was purified by column
chromatography and the desired product of
2,6-di(hex-1-yn-1-yl)-N.sub.1,N.sub.5-dipentylnaphthalene-1,5-diamine
was obtained (50%). LRMS (ESI): Calcd. For C.sub.32H.sub.46N.sub.2:
458.3661. Found: 458.4.
Example 16
2,7-dibutyl-3,8-dipentyl-3,8-dihydroindolo[7,6-g]indole
##STR00067##
[0155] In an dried pressure tube, to a solution of
2,6-di(hex-1-yn-1-yl)-N.sub.1,N.sub.5-dipentylnaphthalene-1,5-diamine
(580 mg) in DMSO (3 mL) was added finely crushed KOH (364 mg). The
resulting reaction mixture was heated at 120.degree. C. for 20 h
and was extracted with ethyl acetate and the combined organic layer
was dried (MgSO.sub.4) and concentrated in vacuo. The residue was
purified by column chromatography on silica gel to give
2,7-dibutyl-3,8-dipentyl-3,8-dihydroindolo[7,6-g]indole (70%). LRMS
(ESI): Calcd. For C.sub.32H.sub.46N.sub.2: 458.3661. Found:
458.4.
Example 17
2,6-dibromonaphthalene-1,5-diol
##STR00068##
[0157] To a suspension of naphthalene-1,5-diol (115.2 g) in
CH.sub.3CN (800 mL) was added DMF solution (400 mL) of NBS (254 g)
dropwise and the mixture was stirred at room temperature and
monitored by GCMS. Water was added quench the reaction. The
resulting precipitate was collected by filtration and washed with
water to give 2,6-dibromonaphthalene-1,5-diol (80%) LRMS (ESI):
Calcd. For C.sub.10H.sub.6Br.sub.2O.sub.2: 317.9614. Found:
317.9.
Example 18
2,6-dibromonaphthalene-1,5-diyl bis(trifluoromethanesulfonate)
##STR00069##
[0159] To a suspension of 2,6-dibromonaphthalene-1,5-diol (4.3 g),
pyridine (6.5 mL) in dichloromethane (130 mL) was slowly added
trifluoromethanesulfonic anhydride (4.7 mL) at 0.degree. C. After
the mixture was stirred at room and monitored by GCMS. Water and
hydrochloric acid (1 M) were added. The resulting mixture was
extracted with dichloromethane and combined organic layer was dried
(MgSO.sub.4) and concentrated in vacuo. The residue was purified by
column chromatography to give 2,6-dibromo-naphthalene-1,5-diyl
bis(trifluoromethanesulfonate) (80%) LRMS (ESI): Calcd. For
C.sub.12H.sub.4Br.sub.2F.sub.6O.sub.6S.sub.2: 582.0850. Found:
581.9.
Example 19
2,6-dibromo-1,5-di(hex-1-yn-1-yl)naphthalene
##STR00070##
[0161] To a degassed solution of 2,6-dibromo-naphthalene-1,5-diyl
bis(trifluoromethane-sulfonate) (3 g) in DMF (36 mL) and
diisopropylamine (36 mL) was added Pd(PPh.sub.3).sub.2Cl.sub.2 (360
mg), CuI (196 mg) and hex-1-yne (1.25 mL). The reaction was stirred
at room temperature and monitored by GCMS. Water and hydrochloric
acid (1 M) were added. The resulting mixture was extracted with
dichloromethane and the combined organic layer was dried
(MgSO.sub.4) and concentrated in vacuo. The residue was purified by
column chromatography on silica gel eluted with hexane to give
2,6-dibromo-1,5-di(hex-1-yn-1-yl)naphthalene (71%) LRMS (ESI):
Calcd. For C.sub.22H.sub.22Br.sub.2: 446.2181. Found: 446.1.
Example 20
1,5-di(hex-1-yn-1-yl)-N2,N6-dipentylnaphthalene-2,6-diamine
##STR00071##
[0163] A solution of 2,6-dibromo-1,5-di(hex-1-yn-1-yl)naphthalene
(1.42 g), t-BuONa (1.42 g), Pd.sub.2dba.sub.3 (146 mg) and
(S)-BINAP (400 mg) in dry toluene (12 mL) was purged with nitrogen
for 5 min. Pentan-1-amine (1.16 mL) was added via a syringe and the
mixture was refluxed under nitrogen for 14 h. After cooling to room
temperature, water was added to the solution and the reaction
mixture was extracted twice with diethyl ether. After the organic
phases were dried over MgSO4, the solvents were removed using a
rotary evaporator. The crude product was purified by column
chromatography and the desired product of
1,5-di(hex-1-yn-1-yl)-N.sub.2,N.sub.6-dipentylnaphthalene-2,6-diamine
was obtained (70%). LRMS (ESI): Calcd. For C.sub.32H.sub.46N.sub.2:
458.3661. Found: 458.4.
Example 21
2,7-dibutyl-1,6-dipentyl-1,6-dihydroindolo[5,4-e]indole
##STR00072##
[0165] In an dried pressure tube, to a solution of
1,5-di(hex-1-yn-1-yl)-N.sub.2,N.sub.6-dipentylnaphthalene-2,6-diamine
(100 mg) in DMSO (3 mL) was added finely crushed KOH (100 mg). The
resulting reaction mixture was heated at 120.degree. C. for 17 h
and was extracted with ethyl acetate and the combined organic layer
was dried (MgSO.sub.4) and concentrated in vacuo. The residue was
purified by column chromatography on silica gel to give
2,7-dibutyl-1,6-dipentyl-1,6-dihydroindolo[5,4-e]indole (50%). LRMS
(ESI): Calcd. For C.sub.32H.sub.46N.sub.2: 458.3661. Found:
458.3.
* * * * *